CN105062502B - Liquid-crystal compounds and its preparation method and use containing penta azacyclo - Google Patents
Liquid-crystal compounds and its preparation method and use containing penta azacyclo Download PDFInfo
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- CN105062502B CN105062502B CN201510484368.4A CN201510484368A CN105062502B CN 105062502 B CN105062502 B CN 105062502B CN 201510484368 A CN201510484368 A CN 201510484368A CN 105062502 B CN105062502 B CN 105062502B
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- 0 C*(C1)C1(C[n]1nnnc1)*1n[n](C)cn1 Chemical compound C*(C1)C1(C[n]1nnnc1)*1n[n](C)cn1 0.000 description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N C[n]1cncc1 Chemical compound C[n]1cncc1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- NGCXHCGUQHIOLZ-UHFFFAOYSA-N C[n]1nccn1 Chemical compound C[n]1nccn1 NGCXHCGUQHIOLZ-UHFFFAOYSA-N 0.000 description 1
- JWAWEQBUZOGIBZ-UHFFFAOYSA-N C[n]1nncc1 Chemical compound C[n]1nncc1 JWAWEQBUZOGIBZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of liquid-crystal compounds and its preparation method and use containing penta azacyclo, the compound has structure as shown in Equation 1, wherein, Y is CF2O or COO, n are 3 or 5, m are 1 or 2；R1、R2、R3、R4For H or F.The synthetic method of the liquid-crystal compounds containing penta azacyclo of the present invention is simple and easy, and raw material is simple and easy to get, and yield is high；With wide mesomorphic phase temperature range, high-k, the advantages of moderate refractive index；In addition, the liquid-crystal compounds of the present invention can be the physical properties such as mesomorphic phase transition temperature, viscosity and index of refraction of the end group to adjust product by using different penta azacyclos, convenient advantage simple with regulation.
Description
Technical field
The invention belongs to liquid crystal material field, and in particular to a kind of five yuan of nitrogen connected using difluoro-methoxy and ester as bridged bond
Heterocyclic liquid-crystal compounds and its preparation method and use, such compound can be by changing end penta azacyclo to its physics
Effective Regulation is carried out with liquid crystal property.
Background technology
In recent decades, the fast development in liquid crystal material field brings the great change of liquid crystal display industry.Liquid crystal display
Device is as important information electronic product, due to its light weight, volume and small power consumption, the leading products as modern displays it
One.
Fluoro liquid crystals has the advantages that viscosity is low, resistivity is high, response speed is very fast, dielectric constant is higher, fits very much
Close the liquid crystal display of TFT driving.Fluorinated liquid crystal, liquid can be reduced by particularly introducing difluoro-methoxy in bridged bond
The fusing point of brilliant molecule, suppresses or eliminates smectic phase, can widen nematic temperature range, increase dielectric constant.While fluorinated liquid crystal
Varied with temperature with high voltage retention, and not.In addition, liquid crystal display requirement driving voltage is low, energy input is small, so
The liquid crystal material of low threshold voltage is needed to use, and such liquid crystal material necessarily requires high dielectric anisotropy.
In recent years, people are by the method for MOLECULE DESIGN, and introducing polarity fluorine atom can improve molecule in liquid crystal molecule
Dielectric anisotropy.At present, the liquid crystal monomer of synthesized high dielectric anisotropy can be divided mainly into phenyl ring is lateral, end and
Bridge chain introduces fluorine atom, by increasing molecular polarity, so as to effectively increase the dielectric anisotropy of molecule.
Heterocycle liquid crystal refers to the cyclic structure liquid-crystal compounds constituted in molecular structure containing carbon atom and non-carbon, ring
In non-carbon be referred to as hetero atom, common hetero atom is aerobic, nitrogen, sulphur etc..The big hetero atom of polarizability can change point
Polarity, the geometric configuration of son are so as to influence the phase transition temperature of liquid crystal.In addition, heteroatomic introducing can influence intermolecular phase
Interaction, so that change the dipole moment size of liquid crystal molecule, direction, dielectric anisotropy feature, meanwhile, the big miscellaneous original of polarizability
Son is introduced can also produce influence to birefringence and mesomorphic facies type of liquid crystal molecule etc., thus, synthesis is miscellaneous containing big polarity
The liquid crystal material of ring is significant to Development of Novel display material.
The content of the invention
The primary and foremost purpose of the present invention is to combine azepine 5-membered ring compounds high polarity and dipole moment, and passes through change
Nitrogen-atoms number in penta azacyclo, its polarity and dipole moment are adjusted, then by connecting liquid crystal structural units, using two
Fluorine methoxyl group or ester be bridged bond there is provided a kind of liquid-crystal compounds containing penta azacyclo, make it have superior liquid crystal property,
Such as：Wide nematic phase range, high-k, moderate refractive index etc..
Another object of the present invention is to provide the synthetic method of the above-mentioned liquid-crystal compounds containing penta azacyclo.
It is still another object of the present invention to provide the purposes of the above-mentioned liquid-crystal compounds containing penta azacyclo, you can is used as liquid crystal
Material monomer component is added in current commercialized mixture liquid crystal to adjust the properties of mixed crystal.
The purpose of the present invention is achieved through the following technical solutions：
A kind of liquid-crystal compounds containing penta azacyclo, with structure as shown in Equation 1：
Wherein, Y is CF2O or COO, n are 3 or 5, m are 1 or 2；
Penta azacyclo is represented, preferably
R1、R2、R3、R4For H or F.
Preferably, n is 3, R1=R2=R3=R4=H,For
Preferably, the above-mentioned liquid-crystal compounds containing penta azacyclo is one kind in following structure：(below structural formula
Letter and number is the numbering of the compound)
In addition, the important intermediate structure being related to during enclosing synthesis above-claimed cpd：
When Y is CF2During O, the synthetic method of the above-mentioned liquid-crystal compounds containing penta azacyclo comprises the following steps：
(1) two sulfosalts shown in formula 2 are dissolved in dichloromethane, are cooled to -70 DEG C, then the change shown in formula 3a is slowly added dropwise
Compound and triethylamine (Et3N dichloromethane solution), stirs and triethylamine trihydrofluoride (Et is added in 1h, 15min3N-3HF), then
Add and contain Br2CH2Cl2Solution；0 DEG C is warmed naturally to, the product shown in formula 4a is obtained after completion of the reaction；
Two sulfosalts shown in formula 2 are according to document (Peer Kirsch, Angew.Chem.Int.Ed.2001,40,1480-
1484) method is synthesized；
The compound shown in two sulfosalts, formula 3a shown in formula 2, Et3N、Et3N-3HF and Br2Mol ratio be 1:(1-2):
(1-2):(3-5):(3-5), preferably 1:1.2:1.4:5:5；
Following reaction occurs for said process：
(2) by the compound shown in formula 4a, penta azacycloCuI、Cs2CO3It is dissolved in dimethylformamide
(DMF) in, 120 DEG C of reaction 24h is heated to, the liquid-crystal compounds shown in formula 5a is obtained after completion of the reaction；
Compound shown in formula 4a,CuI and Cs2CO3Mol ratio be 1:(1-2):(0.2-0.4):(1-2),
It is preferred that 1:1.4:0.2:2；
Following reaction occurs for the process：
In described formula 2, n is 3 or 5；M is 1 or 2；
In described formula 3a, R1、R2、R3、R4For H or F；Preferably, R1=R2=R3=R4=H；
DescribedFor
Step (1) is described to be warmed naturally to 0 DEG C, reaction solution is poured into 30%NaOH solution after completion of the reaction, adjusts pH
It is worth for 5~8, diatomite filtering, CH2Cl2Extraction, is washed, and is dried；Decompression removes solvent, does leacheate with petroleum ether and is obtained through column chromatography
It is white solid to the compound shown in formula 4a；Described is to use water, saturated common salt water washing successively by organic layer washing；Institute
The drying stated is to use anhydrous Na2SO4Dry.
Step (2) is described after completion of the reaction, cooling, CH2Cl2Extracting and washing, is dried；Decompression removes solvent, with petroleum ether/second
Acetoacetic ester mixed solvent obtains the compound shown in formula 5a through column chromatography, is white solid；Described washing organic layer is successively
With water, saturated common salt water washing；Described drying is to use anhydrous Na2SO4Dry；Described petrol ether/ethyl acetate mixed solvent
In, the volume ratio of petroleum ether and ethyl acetate is 5:1.
The synthetic method on difluoro-methoxy bridged bond mainly has two kinds at present：One is direct fluorination, using fluorization agent such as
SF4, DAST etc.；Two be indirect method, i.e. oxidation-desulfurization fluoride process.
Fluorination reagent SF4, DAST has that toxicity is big, extremely active, corrosivity is strong due to it, low yield, is unfavorable for target
The defects such as the separation of product, limit the use of this method.
The present invention above-mentioned difluoro-methoxy bridge chain intermediate 3CCABr, 3CCANO2It is the oxygen according to reports such as Kirch
Change-desulfurization fluoride process synthesis, then it regard nitro compound zinc powder and ammonium chloride as solution in methanol and tetrahydrofuran again
Under conditions of be reduced into aromatic amine compound 3CCANH2。
Above-mentioned synthesis 5a method is ullmann reaction.The use of transition metal-catalyzed ullmann reaction is synthesis C-N keys
Important method.Although there is many synthetic methods to be reported at present, but still it is defective, such as：High cost, to air, water sensitive, or
Need special part.
The key factor of influence ullmann reaction has：1：N arylation reaction condition is harsh, and to the universality of substrate
It is not high；2：C-N is coupled has competition between C-C couplings.
The present invention explores to a gentle and effective method to synthesize target coupled product.Catalysis is used as using CuI
Agent, Cs2CO3Make alkali, DMF makees solvent and 24h is reacted at 120 DEG C, and yield is high.Wherein, when(such as chemical combination during for tetrazole ring
Thing CF2ON-1234), mixture is obtained using ullmann reaction, TLC tracking there are 8 points, and is difficult to separating-purifying.Therefore, originally
Invention devises new synthetic method, uses aromatic amine compound 3CCANH2, triethyl orthoformate, sodium azide directly synthesizes end
Hold the difluoro-methoxy liquid crystal molecule for tetrazole.
When Y is CF2O、During for tetrazole ring, the synthetic method of the above-mentioned liquid-crystal compounds containing penta azacyclo
Comprise the following steps：
(1) two sulfosalts shown in formula 2 are dissolved in dichloromethane, are cooled to -70 DEG C, then the change shown in formula 3a is slowly added dropwise
Compound and triethylamine (Et3N dichloromethane solution), stirs and Et is added in 1h, 15min3N-3HF, is added containing Br2CH2Cl2
Solution；0 DEG C is warmed naturally to, the product as shown in formula 4b is obtained after completion of the reaction；
The compound shown in two sulfosalts, formula 3b shown in formula 2, Et3N、Et3N-3HF and Br2Mol ratio be 1:(1-2):
(1-2):(3-5):(3-5), preferably 1:1.2:1.4:5:5；
Two sulfosalts shown in formula 2 are according to document (Peer Kirsch, Angew.Chem.Int.Ed.2001,40,1480-
1484) method is synthesized；
Following reaction occurs for said process：
(2) by the compound shown in formula 4b, NH4Cl is dissolved in the mixed solution of methanol and tetrahydrofuran, adds zinc powder, room
Temperature stirring 24h, obtains the product shown in formula 5b after completion of the reaction；
Compound, Zn and NH shown in formula 4b4Cl mol ratio is 1:(4-6):(4-6), preferably 1:6:6；
Following reaction occurs for said process：
(3) compound shown in formula 5b, triethyl orthoformate, sodium azide are placed in tube sealing, it is rapid under fume hood
Acetic acid is added, 80 DEG C of reaction 4h is warming up to, the liquid-crystal compounds as shown in formula 6b is obtained after completion of the reaction；
The mol ratio of compound, triethyl orthoformate and sodium azide shown in formula 5b is 1:(2-3):(1-1.5), preferably
1:3:1.1；
Following reaction occurs for said process：
In described formula 2, n is 3 or 5；M is 1 or 2；
In described formula 3b, R1、R2、R3、R4For H or F；Preferably, R1=R2=R3=R4=H；
Step (1) is described to be warmed naturally to 0 DEG C, reaction solution is poured into 30%NaOH solution after completion of the reaction, adjusts pH
It is worth for 5~8, diatomite filtering, CH2Cl2Extraction, is washed, and is dried；Decompression removes solvent, and leacheate is done with petroleum ether/dichloromethane
The compound shown in formula 4b is obtained through column chromatography, is white solid.Described is to use water, saturated common salt successively by organic layer washing
Water washing；Described drying is to use anhydrous Na2SO4Dry；The volume ratio of petroleum ether/dichloromethane is 1:1.
Step (2) is described after completion of the reaction, and diatomite filtering, revolving removes solvent, molten with petroleum ether/dichloromethane mixing
Agent obtains the compound shown in formula 5b, white solid through column chromatography.The volume ratio of petroleum ether/dichloromethane is 1:1.
Step (3) is described after completion of the reaction, is cooled to room temperature, is slowly added to sodium chloride solution, adds proper amount of sodium carbonate
Produced to without gas, CH2Cl2Extraction, is washed, and is dried；Decompression removes solvent, is recrystallized to give the liquid-crystal compounds shown in formula 6b, in vain
Color solid.Described is to use water, saturated common salt water washing successively by organic layer washing；Described drying is to use anhydrous Na2SO4It is dry
It is dry.
When Y is COO, the synthetic method of the above-mentioned liquid-crystal compounds containing penta azacyclo comprises the following steps：
(1) by the compound shown in formula 6, penta azacycloCuI、Cs2CO3It is dissolved in DMF, is heated to 120
DEG C, 24h is reacted, the product shown in formula 7 is obtained after completion of the reaction；
Compound shown in formula 6,CuI and Cs2CO3Mol ratio be 1:(1-2):(0.2-0.4):(1-2),
It is preferred that 1:2:0.2:2；
Following reaction occurs for said process：
(2) by BBr3It is dissolved in CH2Cl2In, add to 0 DEG C of the CH containing compound shown in formula 72Cl2In solution, 3- is reacted
4h, obtains product as shown in Equation 8 after completion of the reaction；
Compound and BBr shown in formula 73Mol ratio be 1:(1-3), preferably 1:2.5；
Following reaction occurs for said process：
(3) by the compound shown in formula 9, the compound shown in formula 8, N, N'- dicyclohexylcarbodiimides (DCC) and 4- bis-
Methylamino pyridine (DMAP) is dissolved in chloroform, is heated to reflux 12h, and LCD compound as shown in Equation 10 is obtained after completion of the reaction
Thing；
The mol ratio of compound and DCC, DMAP shown in formula 8 is 1:(1-2):(0.2-0.4), preferably 1:1.2:0.2；
In order that reaction is carried out thoroughly, the amount of formula 9 is excessive, and its consumption is usually 1.2 times of formula 8, it can be understood as
Formula 8 is 1 with formula 9, DCC, DMAP mol ratio:(1-2):(1-2):(0.2-0.4)；
Following reaction occurs for said process：
In described formula 9, n is 3 or 5；M is 1 or 2；
In described formula 6, R1、R2、R3、R4For H or F；Preferably, R1=R2=R3=R4=H；
For
Step (1) is described after completion of the reaction, cooling, CH2Cl2Extracting and washing, is dried, and decompression removes solvent, with petroleum ether, stone
Oily ether/ethyl acetate mixed solvent gradient elution obtains the compound shown in formula 7 through column chromatography, according toDifference obtain
Transparent pale pink crystal or transparency liquid or white solid.Described washing organic layer is to use water, saturated common salt water washing successively；
Described drying is to use anhydrous Na2SO4Dry；Described petrol ether/ethyl acetate in the mixed solvent, petroleum ether and ethyl acetate
Volume ratio be respectively 1:1；
Step (2) is described after completion of the reaction, and Na is used successively2CO3、NH4Cl, the washing of saturation NaCl solution, ethyl acetate extraction
Take, wash, dry, decompression removes solvent.Obtained with the gradient elution of petrol ether/ethyl acetate mixed solvent through column chromatography shown in formula 8
Compound, according toDifference obtain yellow or transparency liquid or white solid.Described washing organic layer is successively
With water, saturated common salt water washing；Described drying is to use anhydrous Na2SO4Dry；Described petrol ether/ethyl acetate mixed solvent
In, the volume ratio of petroleum ether and ethyl acetate is 5:1；
Step (3) is described after completion of the reaction, and white solid is obtained such as through column chromatography with petrol ether/ethyl acetate mixed solvent
Liquid-crystal compounds shown in formula 10；Described N, N'- dicyclohexylcarbodiimide (DCC) are as dehydrating agent；Described 4- bis-
Methylamino pyridine (DMAP) is as catalyst；Described petrol ether/ethyl acetate in the mixed solvent, petroleum ether and ethyl acetate
Volume ratio be 5:1.
The liquid-crystal compounds containing penta azacyclo that the present invention is included can be used as liquid crystal display material, be added it to
In liquid crystal mixed crystal, clearing point, birefringence, nematic temperature range, the dielectric constant of mixed crystal can be adjusted.
The present invention has the following advantages and effect relative to prior art：
1st, the synthetic method of the liquid-crystal compounds containing penta azacyclo of the invention is simple and easy, and raw material is simple and easy to get, yield
It is high.
2nd, liquid-crystal compounds containing penta azacyclo of the invention has wide mesomorphic phase temperature range, high-k, fits
In refractive index the advantages of.
3rd, liquid-crystal compounds containing penta azacyclo of the invention can be terminal groups by using different penta azacyclos
The physical properties such as mesomorphic phase transition temperature, viscosity and index of refraction of the group to adjust product, convenient advantage simple with regulation.
Brief description of the drawings
Fig. 1 is product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl miaow of embodiment 1
Azoles (CF2ON-13 differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates)).
Fig. 2 be embodiment 2 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3 ,-triazole (CF2ON-123 differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates)).
Fig. 3 be embodiment 3 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,4 ,-triazole (CF2ON-124 differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates)).
Fig. 4 be embodiment 4 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3,4- tetrazoles (CF2ON-1234 differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates)).
Fig. 5 is product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol ester of embodiment 5
(COON-13) differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates).
Fig. 6 is product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- triazoles of embodiment 6
The differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates) of base phenol ester (COON-123).
Fig. 7 is product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- triazoles of embodiment 7
The differential scanning calorimeter collection of illustrative plates (DSC collection of illustrative plates) of base phenol ester (COON-124).
Fig. 8 is product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl miaow of embodiment 1
Azoles (CF2ON-13 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively the compound at 183 DEG C, 231 DEG C
POM collection of illustrative plates.
Fig. 9 be embodiment 2 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3 ,-triazole (CF2ON-123 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively that the compound exists
180 DEG C, 234 DEG C of POM collection of illustrative plates.
Figure 10 be embodiment 3 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,4 ,-triazole (CF2ON-124 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively that the compound exists
173 DEG C, 198 DEG C of POM collection of illustrative plates.
Figure 11 be embodiment 4 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3,4- tetrazoles (CF2ON-1234 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively the compound
In 191 DEG C, 240 DEG C of POM collection of illustrative plates.
Figure 12 is product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol ester of embodiment 5
(COON-13) petrographic microscope collection of illustrative plates (POM collection of illustrative plates)；Wherein, a, b are respectively that the compound is schemed in 144 DEG C, 179 DEG C of POM
Spectrum.
Figure 13 is the nitrogen of product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- three of embodiment 6
The petrographic microscope collection of illustrative plates (POM collection of illustrative plates) of oxazolyl phenol ester (COON-123)；Figure 13 is POM collection of illustrative plates of the compound at 153 DEG C.
Figure 14 is the nitrogen of product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- three of embodiment 7
The petrographic microscope collection of illustrative plates (POM collection of illustrative plates) of oxazolyl phenol ester (COON-124)；Figure 14 is POM collection of illustrative plates of the compound at 155 DEG C.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenylimidazole (CF2ON-13 synthesis),
Comprise the following steps：
The synthesis of (1) two sulfosalt
By 4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid, (structure is)
(5.18g, 0.02mol), toluene (12mL), isooctane (12mL) are placed in three neck round bottom and stirred, and nitrogen protection is lower to be added
Dimercaptopropane (2.6mL, 0.026mol), is warming up to 50 DEG C, and trifluoromethanesulfonic acid (2.4mL, 0.024mol) is added dropwise, and is heated after dripping off
To 102-104 DEG C.After reaction terminates, system is cooled to 90-70 DEG C, 15mL isopropyl ethers are slowly added to, separated out after white crystal,
Place refrigerator stand-by.
(2) 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) bromobenzenes
Dichloromethane of two sulfosalts (9.76g, 0.02mol) in (1) after water removal is dissolved, -70 DEG C are cooled to, slowly
P bromophenol (4.15g, 0.02mol), the dichloromethane solution of triethylamine (3.3mL, 0.022mol) is added dropwise, is stirred after dripping
Triethylamine trihydrofluoride (16.2mL, 0.1mol) is added in 1h, 15min, bromine (5.13mL, 0.1mol) dichloromethane is slowly added dropwise
Alkane solution, 1h is stirred after dripping.- 5-0 DEG C are warmed naturally to, reaction solution is poured into 30% sodium hydroxide solution with ice cube
In, and adjust pH value 5~8.Diatomite is filtered, and is extracted, washing, anhydrous sodium sulfate drying.Finally column chromatography is carried out with petroleum ether
Obtain white solid, yield 35%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):7.41 (d, J=9.0Hz, 2H),
7.02 (d, J=8.9Hz, 2H), 2.00 (s, 3H), 1.82 (d, J=13.6Hz, 2H), 1.69 (d, J=15.3Hz, 4H), 1.29
(dt, J=14.1,10.4Hz, 4H), 1.15-1.08 (m, 3H), 0.99 (dd, J=25.2,12.6Hz, 6H), 0.85 (t, J=
7.3Hz,5H).19F NMR(376MHz,CDCl3)δ(ppm):- 78.26 (d, J=8.2Hz, 2F) .MS (ESI) m/z:428(M+) .Anal.Calcd (%) for:C22H31BrF2O:(428.15)：C,61.54；H,7.28.Found:C,61.64；H,
7.26.N<0.30%. infer that the structure of product is as follows accordingly, be 4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl) difluoro first
Oxy-1-bromobenzene.
(3) 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenylimidazole (CF2ON-13 conjunction)
Into
By the product (0.428g, 0.001mol) in (2), CuI (0.039g, 0.0002mol), Cs2CO3(0.63g,
0.002mol) and imidazoles (0.0952g, 0.0014mol) is dissolved in DMF, 120 DEG C are heated to, 24h is reacted.Cooled and filtered, second
Acetoacetic ester is extracted, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) column chromatography is carried out to obtain
White solid, yield 80%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):7.80(s,1H),7.34(d,J
=9.0Hz, 2H), 7.28 (d, J=8.9Hz, 2H), 7.24 (s, 1H), 7.20 (s, 1H), 2.05 (t, J=11.2Hz, 3H),
1.85 (d, J=12.1Hz, 2H), 1.74 (t, J=14.4Hz, 4H), 1.43 (s, 2H), 1.26 (s, 4H), 1.17-1.12 (m,
3H), 1.01 (d, J=55.9Hz, 5H), 0.86 (d, J=7.4Hz, 4H)19F NMR(CDCl3)δ(ppm):- 78.16 (d, J=
8.2Hz,2F).MS(ESI)m/z:416(M+) .Anal.Calcd (%) for:C25H34F2N2O:C,72.08；H,8.23；N,
6.73.Found:C,72.10；H,8.21；N,6.38.
Infer that the structure of product is as follows accordingly, be 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy]
Phenylimidazole.
Embodiment 2
4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,3,-triazole
(CF2ON-123 synthesis), comprises the following steps：
The synthesis of (1) two sulfosalt
Be the same as Example 1.
(2) 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) bromobenzenes
Dichloromethane of two sulfosalts (9.76g, 0.02mol) in (1) after water removal is dissolved, -70 DEG C are cooled to, slowly
P bromophenol (4.15g, 0.02mol), the dichloromethane solution of triethylamine (3.3mL, 0.022mol) is added dropwise, is stirred after dripping
Triethylamine trihydrofluoride (16.2mL, 0.1mol) is added in 1h, 5min, the dichloromethane of bromine (5.13mL, 0.1mol) is added dropwise slowly
Solution, 1h is stirred after dripping.- 5-0 DEG C are warmed naturally to, reaction solution is poured into 30% sodium hydroxide solution with ice cube
In, and adjust pH value 5~8.Diatomite is filtered, and is extracted, washing, anhydrous sodium sulfate drying.Finally column chromatography is carried out with petroleum ether
Obtain white solid, yield 35%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):7.41 (d, J=9.0Hz, 2H),
7.02 (d, J=8.9Hz, 2H), 2.00 (s, 3H), 1.82 (d, J=13.6Hz, 2H), 1.69 (d, J=15.3Hz, 4H), 1.29
(dt, J=14.1,10.4Hz, 4H), 1.15-1.08 (m, 3H), 0.99 (dd, J=25.2,12.6Hz, 6H), 0.85 (t, J=
7.3Hz,5H).19F NMR(376MHz,CDCl3)δ(ppm):- 78.26 (d, J=8.2Hz, 2F) .MS (ESI) m/z:428(M+) .Anal.Calcd (%) for:C22H31BrF2O:(428.15)：C,61.54；H,7.28.Found:C,61.64；H,
7.26.N<0.30%. infer that the structure of product is as follows accordingly, be 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl) difluoros
Methoxyl group) bromobenzene.
(3) 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,3,-triazole
(CF2ON-123 synthesis)
By the product (0.428g, 0.001mol) in (2), CuI (0.039g, 0.0002mol), Cs2CO3(0.63g,
0.002mol) and 1,2,3- triazoles (0.0966g, 0.0014mol) are dissolved in DMF, are heated to 120 DEG C, react 24h.Cooling
After filter, ethyl acetate extraction, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) post is carried out
Chromatography obtains two products, is white solid, yield respectively accounts for 45% or so.
The structural characterization data of one of product are：1H NMR(400MHz,CDCl3)δ(ppm):7.95 (d, J=
1.0Hz, 1H), 7.84 (d, J=1.0Hz, 1H), 7.70 (d, J=9.0Hz, 2H), 7.32 (d, J=8.5Hz, 2H), 2.06 (d,
J=9.9Hz, 2H), 1.77 (dd, J=35.1,18.5Hz, 6H), 1.36-1.27 (m, 7H), 1.18-1.00 (m, 9H), 0.87
(t, J=7.3Hz, 3H)19F NMR(CDCl3)δ(ppm):- 78.17 (d, J=8.1Hz, 2F) .MS (EI) m/z:417(M)+
.Anal.Calcd for C24H33F2N3O:C,69.04；H,7.97；N,10.06；found:C,69.09；H,7.97；N,
10.02.
Infer that the structure of product is as follows accordingly, be 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy]
Phenyl -1H-1,2,3,-triazole (CF2ON-123)
The structural characterization data of another product are：1H NMR(400MHz,CDCl3)δ(ppm):8.04 (d, J=9.1Hz,
2H), 7.80 (d, 1.1Hz, 2H), 7.28 (d, J=8.0Hz, 2H), 2.06 (d, J=11.6Hz, 3H), 1.80 (dd, J=
38.1,13.2Hz, 7H), 1.31-1.03 (m, 12H), 0.87 (t, J=7.3Hz, 5H)19F NMR(CDCl3)δ(ppm):-
78.07 (d, J=8.2Hz, 2F) .MS (EI) m/z:417(M)+.Anal.Calcd for C24H33F2N3O:C,69.04；H,
7.97；N, 10.06%；found:C,68.96；H,7.92；N,10.10.
Infer that the structure of product is as follows accordingly, 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene
Base -1H-1,2,5,-triazole.
Embodiment 3
4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,4,-triazole
(CF2ON-124 synthesis), comprises the following steps：
The synthesis of (1) two sulfosalt
Be the same as Example 1.
(2) 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) bromobenzenes
Dichloromethane of two sulfosalts (9.76g, 0.02mol) in (1) after water removal is dissolved, -70 DEG C are cooled to, slowly
P bromophenol (4.15g, 0.02mol), the dichloromethane solution of triethylamine (3.3mL, 0.022mol) is added dropwise, is stirred after dripping
Triethylamine trihydrofluoride (16.2mL, 0.1mol) is added in 1h, 15min, bromine (5.13mL, 0.1mol) dichloromethane is slowly added dropwise
Alkane solution, 1h is stirred after dripping.- 5-0 DEG C are warmed naturally to, reaction solution is poured into 30% sodium hydroxide solution with ice cube
In, and adjust pH=5~8.Diatomite is filtered, and is extracted, washing, anhydrous sodium sulfate drying.Finally column chromatography is carried out with petroleum ether
Obtain white solid, yield 35%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):7.41 (d, J=9.0Hz, 2H),
7.02 (d, J=8.9Hz, 2H), 2.00 (s, 3H), 1.82 (d, J=13.6Hz, 2H), 1.69 (d, J=15.3Hz, 4H), 1.29
(dt, J=14.1,10.4Hz, 4H), 1.15-1.08 (m, 3H), 0.99 (dd, J=25.2,12.6Hz, 6H), 0.85 (t, J=
7.3Hz,5H).19F NMR(376MHz,CDCl3)δ(ppm):- 78.26 (d, J=8.2Hz, 2F) .MS (ESI) m/z:428(M+) .Anal.Calcd (%) for:C22H31BrF2O:(428.15)：C,61.54；H,7.28.Found:C,61.64；H,
7.26.N<0.30%.
Infer that the structure of product is as follows accordingly, be 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl) difluoromethoxies
Base) bromobenzene.
(3) 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,4,-triazole
(CF2ON-124 synthesis)
By the product (0.428g, 0.001mol) in (2), CuI (0.039g, 0.0002mol), Cs2CO3(0.63g,
0.002mol) and 1,2,4- triazoles (0.0966g, 0.0014mol) are dissolved in DMF, are heated to 120 DEG C, react 24h.Cooling
After filter, ethyl acetate extraction, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) post is carried out
Chromatography obtains white solid product.
The structural characterization data of product are：1H NMR(CDCl3)δ(ppm):8.10 (s, 1H), 7.64 (d, J=8.5Hz,
2H), 7.30 (d, J=8.1Hz, 2H), 7.25 (s, 1H), 2.05 (t, J=10.4Hz, 3H), 1.90-1.66 (m, 8H), 1.34-
(t, J=7.2Hz, the 5H) of 1.28 (m, 5H), 1.02 (ddd, J=18.8,16.4,12.1Hz, 6H), 0.8719F NMR(CDCl3)
δ(ppm):- 78.16 (d, J=8.1Hz, 2F) .MS (EI) m/z:417(M)+.Anal.Calcd for C24H33F2N3O:C,
69.04；H,7.97；N,10.06；found:C,68.86；H,7.98；N,9.89.
Infer that the structure of product is as follows accordingly, 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene
Base -1H-1,2,4,-triazole.
Embodiment 4
4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,3,4- tetrazoles
(CF2ON-1234 synthesis), comprises the following steps：
The synthesis of (1) two sulfosalt
Be the same as Example 1.
(2) 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) nitrobenzene
Dichloromethane of two sulfosalts (9.76g, 0.02mol) in (1) after water removal is dissolved, -70 DEG C are cooled to, slowly
P-nitrophenol (2.78g, 0.02mol), the dichloromethane solution of triethylamine (3.3mL, 0.022mol) is added dropwise, is stirred after dripping
Mix and triethylamine trihydrofluoride (16.2mL, 0.1mol) is added in 1h, 15min, bromine (5.13mL, 0.1mol) dichloro is slowly added dropwise
Dichloromethane, 1h is stirred after dripping.- 5-0 DEG C are warmed naturally to, it is molten that reaction solution is poured into 30% sodium hydroxide with ice cube
In liquid, and adjust pH value 5~8.Diatomite is filtered, and is extracted, washing, anhydrous sodium sulfate drying.Post layer is finally carried out with petroleum ether
Analysis obtains white solid, yield 35%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):8.21 (d, J=2.6Hz, 2H),
7.32 (s, 2H), 2.04 (d, J=9.2Hz, 3H), 1.86 (d, J=7.8Hz, 2H), 1.79-1.64 (m, 4H), 1.40-1.20
(m, 4H), 1.22-0.95 (m, 9H), 0.88 (d, J=5.9Hz, 5H)19F NMR(CDCl3)δ:(ppm):- 78.64 (d, J=
7.9Hz,2F).MS(ESI)m/z:434.3(M++K+).
Infer that the structure of product is as follows accordingly, 1- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) nitre
Base benzene
(3) 4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) aniline
By the product 1- of (2) (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) nitrobenzene (3.96g,
0.01mol), zinc powder (3.92g, 0.06mol), ammonium chloride (3.21g, 0.06mol), methanol (60mL) and tetrahydrofuran (30mL)
It is put into tube sealing and stirs 24h at room temperature.After completion of the reaction, mixture is filtered with 2.5g diatomite.Revolving removes organic matter, uses
Petroleum ether/dichloromethane (V:V=1:2) (Rf=0.4) carries out column chromatography as eluant, eluent, obtains the target of white solid product
Product.Yield 94%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):6.94 (d, J=8.4Hz, 2H),
6.62 (d, J=8.1Hz, 2H), 3.59 (s, 2H), 2.01 (t, J=16.7Hz, 3H), 1.83 (d, J=11.9Hz, 2H), 1.73
(t, J=14.7Hz, 4H), 1.31 (m, 4H), 1.18-1.10 (m, 3H), 1.00 (m, 6H), 0.97-0.79 (m, 5H)19F NMR
(CDCl3)δ(ppm):- 78.14 (d, J=8.3Hz, 2F) .MS (ESI) m/z:366.1(M+H)+.
Infer that the structure of product is as follows accordingly, 4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy) aniline
(4) 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl -1H-1,2,3,4- tetrazoles
(CF2ON-1234)
By 3CCANH2(0.183g, 0.005mol), triethyl orthoformate (0.22g, 0.0015mol), sodium azide
(0.036g, 0.00055mol) is added in acetic acid (10mL), is heated to 80 DEG C of reaction 4h.Room temperature is cooled to, is added in right amount
Na2CO3Produced to without gas.Dichloromethane (50mL) is extracted, and is washed (3 × 100mL), anhydrous sodium sulfate drying, and revolving is except molten
Agent, with petroleum ether/dichloromethane (V:V=1:5) column chromatography is carried out as eluant, eluent, obtains the target production of white solid product
Thing, yield 89%.
Structural characterization data to product are：1H NMR(400MHz,CDCl3)δ(ppm):8.89(s,1H),7.61(d,J
=8.9Hz, 2H), 7.32 (d, J=8.8Hz, 2H), 2.00 (d, J=11.6Hz, 2H), 1.80 (d, J=11.7Hz, 2H),
(dd, J=14.9,7.6Hz, the 5H) of 1.73-1.63 (m, 4H), 1.36-1.17 (m, 5H), 1.11-0.88 (m, 9H), 0.8019F
NMR(CDCl3)δ(ppm):- 78.26 (d, J=8.3Hz, 2F) .MS (ESI) m/z:435.44(M+H)+.Anal.Calcd for
C23H32F2N4O:C,66.00；H,7.71；N,13.39；found:C,66.01；H,7.64；N,13.39.
Infer that the structure of product is as follows accordingly, 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene
Base -1H-1,2,3,4- tetrazoles (CF2ON-1234)
Embodiment 5
The synthesis of 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol ester (COON-13), including with
Lower step：
(1) synthesis of 1-H- (4- methoxyphenyls) imidazoles
Will to methoxybromobenzene (1.87g, 0.01mol), imidazoles (1.36g, 0.02mol), CuI (0.38g,
0.002mol)、Cs2CO3(6.52g, 0.02mol) is dissolved in DMF, is heated to 120 DEG C, reacts 24h.Cooled and filtered, acetic acid second
Ester is extracted, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) carry out column chromatography and obtain white
Crystal, yield 76%.
(2) 4- (1H- imidazoles) phenol
The product (1.75g, 0.01mol) of (1) is taken to be dissolved in CH2Cl2, 0 DEG C is cooled to, 15min is stirred, BBr is slowly added dropwise3
The CH of (2.32mL, 0.025mol)2Cl2Solution.After dripping, 4h is reacted at room temperature.
After completion of the reaction, reaction solution is used into sodium acid carbonate, ammonium chloride, salt water washing respectively.Organic layer anhydrous sodium sulfate
Dry, revolving removes CH2Cl2, with petrol ether/ethyl acetate (V:V=1:1) column chromatography is carried out as eluant, eluent, obtains white solid
Body, yield is 65.17%.
(3) synthesis of 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol ester
By 4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid, (structure is)
(3.024g, 0.012mol), 4- (1H- imidazoles) phenol (1.6g, 0.01mol), N, N'- dicyclohexylcarbodiimides (DCC)
(2.472g, 0.012mol), DMAP (DMAP) (0.244g, 0.002mol), is dissolved in CHCl3, it is heated to reflux
12h, adds 50mL dichloromethane after completion of the reaction, then uses water successively, and saturated common salt water washing is multiple.Organic layer anhydrous slufuric acid
Sodium is dried, and revolving removes dichloromethane, with petrol ether/ethyl acetate (V:V=1:1) column chromatography is carried out as eluant, eluent, obtained
White solid, yield 86%.
Structural characterization data to product are：1H NMR(500MHz,(CD3)2SO)δ(ppm):8.26(s,1H),7.75
(s, 1H), 7.68 (d, J=8.9Hz, 2H), 7.25 (d, J=8.9Hz, 2H), 7.12 (s, 1H), 1.71 (s, 3H), 1.62
(ddd, J=10.4,7.7,3.8Hz, 3H), 1.25 (d, J=12.9Hz, 4H), 1.07 (ddd, J=29.1,20.6,6.8Hz,
10H),0.95–0.79(m,7H).MS(ESI)m/z:394(M+) .Anal.Calcd (%) for:C25H34N2O2:C,76.10；
H,8.69；N,7.10；Found:C,76.06；H,8.78；N,7.15.
Infer that the structure of product is as follows accordingly, be 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals benzene
Phenolic ester.
Embodiment 6
4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- triazol radicals phenol ester (COON-123)
Or the conjunction of 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,5- triazol radicals phenol ester (COON-125)
Into comprising the following steps：
(1) synthesis of 4- methoxyphenyls -1H-1,2,3- triazoles and (4- methoxyphenyl -1H-1,2,5- triazoles)
Will to methoxybromobenzene (1.87g, 0.01mol), 1,2,3- triazole (1.38g, 0.02mol), CuI (0.38g,
0.002mol)、Cs2CO3(6.52g, 0.02mol) is dissolved in DMF, is heated to 120 DEG C, reacts 24h.Cooled and filtered, acetic acid second
Ester is extracted, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) carry out column chromatography and obtain two
White solid product, 4- methoxyphenyls -1H-1,2,3- triazoles and 4- methoxyphenyls -1H-1,2,5- triazole yields are each
Account for 45% or so.
4- methoxyphenyl -1H-1,2,3- triazoles
4- methoxyphenyl -1H-1,2,5- triazoles
(2) synthesis of 4- (1H-1,2,3- triazoles) phenol or 4- (1H-1,2,5- triazoles) phenol
The product (1.75g, 0.01mol) of (1) is taken, CH is dissolved in2Cl2, 0 DEG C is cooled to, 15min is stirred, BBr is slowly added dropwise3
The CH of (2.32mL, 0.025mol)2Cl2Solution, after dripping, reacts at room temperature 4h.After completion of the reaction, reaction solution is used into carbon respectively
Sour hydrogen sodium, ammonium chloride, salt water washing.Organic layer anhydrous sodium sulfate drying, revolving removes CH2Cl2, use petrol ether/ethyl acetate
(V:V=1:1) column chromatography is carried out as eluant, eluent, obtains white solid, yield is respectively 65%, 66%.
4- (1H-1,2,3- triazoles) phenol
4- (1H-1,2,5- triazoles) phenol
(3) 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- triazol radicals phenol esters or 4- (4-
(trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,5- triazol radical phenol esters synthesis
By 4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid, (structure is)
(3.024g, 0.012mol), 4- (1H-1,2,3- triazoles) phenol or 4- (1H-1,2,5- triazoles) phenol (1.61g,
0.01mol), N, N'- dicyclohexylcarbodiimide (DCC) (2.472g, 0.012mol), DMAP (DMAP)
(0.244g, 0.002mol), is dissolved in CHCl3, 12h is heated to reflux, 50mL dichloromethane is added after completion of the reaction, then use successively
Water, saturated common salt water washing is multiple.Organic layer anhydrous sodium sulfate drying, revolving removes dichloromethane, with petroleum ether/acetic acid second
Ester (V:V=5:1) column chromatography is carried out as eluant, eluent, obtains white solid, yield is respectively 92%, 94%.
Structural characterization data to product are：1H NMR(CDCl3)δ(ppm):8.02-7.94 (m, 1H), 7.88 (d, J=
0.8Hz, 1H), 7.77 (d, J=8.9Hz, 2H), 7.27 (d, J=8.9Hz, 2H), 2.20 (d, J=13.7Hz, 3H), 1.80-
1.75(m,6H),1.34–1.28(m,6H),1.18–1.13(m,7H),0.91–0.88(m,6H).MS(EI)m/z:395(M)+
.Anal.Calcd for C24H33N3O2:C,72.88；H,8.41；N,10.62；found:C,73.21；H,8.83；N,
10.45.
Infer that the structure of product is as follows accordingly, be 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,
3- triazol radical phenol esters
Structural characterization data to product are：1H NMR(CDCl3)δ(ppm):8.08 (d, J=9.0Hz, 2H), 7.80 (s,
2H), 7.19 (d, J=9.0Hz, 2H), 1.87-1.71 (m, 8H), 1.30 (ddd, J=15.7,13.0,7.8Hz, 6H), 1.11
(dd, J=24.1,15.4Hz, 8H), 0.87 (t, J=7.3Hz, 5H) .MS (EI) m/z:395(M)+.Anal.Calcd for
C24H33N3O2:C,72.88；H,8.41；N,10.62；found:C,72.78；H,8.63；N,10.46.
Infer that the structure of product is as follows accordingly, be 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,
5- triazol radical phenol esters
Embodiment 7
4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- triazol radicals phenol ester (COON-124)
Synthesis, comprise the following steps：
(1) synthesis of 4- methoxyphenyls -1H-1,2,4- triazoles
Will to methoxybromobenzene (1.87g, 0.01mol), 1,2,4- triazole (1.38g, 0.02mol), CuI (0.38g,
0.002mol)、Cs2CO3(6.52g, 0.02mol) is dissolved in DMF, is heated to 120 DEG C, reacts 24h.Cooled and filtered, acetic acid second
Ester is extracted, washing, anhydrous sodium sulfate drying.Finally use petroleum ether：Ethyl acetate (V:V=5:1) carry out column chromatography and obtain white
Solid product, yield 78%.
(2) synthesis of 4- (1H-1,2,4- triazoles) phenol
The product (1.75g, 0.01mol) of (1) is taken, CH is dissolved in2Cl2, 0 DEG C is cooled to, 15min is stirred, BBr is slowly added dropwise3
The CH of (2.32mL, 0.025mol)2Cl2Solution, after dripping, reacts at room temperature 4h.After completion of the reaction, reaction solution is used into carbon respectively
Sour hydrogen sodium, ammonium chloride, salt water washing.Organic layer anhydrous sodium sulfate drying, revolving removes CH2Cl2, use petrol ether/ethyl acetate
(V:V=1:1) column chromatography is carried out as eluant, eluent, obtains white solid, yield 66%.
(3) synthesis of 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- triazol radical phenol esters
By 4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid, (structure is)
(3.024g, 0.012mol), 4- (1H-1,2,4- triazoles) phenol (1.61g, 0.01mol), N, N'- dicyclohexyls carbon two is sub-
Amine (DCC) (2.472g, 0.012mol), DMAP (DMAP) (0.244g, 0.002mol), are dissolved in CHCl3, heating
Flowed back 12h, and 50mL dichloromethane is added after completion of the reaction, then uses water successively, and saturated common salt water washing is multiple.Organic layer is with anhydrous
Sodium sulphate is dried, and revolving removes dichloromethane, with petrol ether/ethyl acetate (V:V=5:1) column chromatography is carried out as eluant, eluent,
White solid is obtained, yield is respectively 93%.
Structural characterization data to product are：1H NMR(CDCl3)δ(ppm):8.51(s,1H),8.08(s,1H),7.66
(d, J=8.9Hz, 2H), 7.20 (d, J=8.9Hz, 2H), 2.15 (d, J=13.5Hz, 2H), 1.81-1.64 (m, 9H), 1.04
(ddd, J=41.0,18.4,7.3Hz, 11H), 0.88-0.81 (m, 7H) .MS (EI) m/z:395(M)+.Anal.Calcd for
C24H33N3O2:C,72.88；H,8.41；N,10.62；found:C,73.22；H,8.84；N,10.46.
Infer that the structure of product is as follows accordingly, be 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,
4- triazol radical phenol esters
Embodiment 8
Embodiment 1-7 product is tested its phase transition temperature with differential scanning calorimetric analysis instrument (DSC).As a result
It is as follows：
As shown in figure 1, product 1-H- (4- (4- (trans- 4- n-propyls cyclohexyl) cyclohexyl) difluoro-methoxies of embodiment 1
Phenyl) imidazoles (CF2ON-13) temperature for being changed into liquid crystalline phase by crystalline phase is 124.5 DEG C, is each to phasic property from liquid crystal phase transition
The temperature of liquid is 233.0 DEG C.
As shown in Fig. 2 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene of embodiment 2
Base -1H-1,2,3,-triazole (CF2ON-123) temperature for being changed into liquid crystalline phase by crystalline phase is 176.3 DEG C, is turned by liquid crystalline phase
It is changed into each temperature to phasic property liquid for 246.0 DEG C.
As shown in figure 3, product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene of embodiment 3
Base -1H-1,2,4,-triazole (CF2ON-124) temperature for being changed into liquid crystalline phase by crystalline phase is 160.6 DEG C, is turned by liquid crystalline phase
It is changed into each temperature to phasic property liquid for 241.7 DEG C.
As shown in figure 4, product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] benzene of embodiment 4
Base -1H-1,2,3,4- tetrazoles (CF2ON-1234 it is) 154 DEG C by the temperature of another crystalline phase of crystallization phase in version, is changed into
The temperature of smectic phase is 169.0 DEG C, and nematic temperature is changed into for 219.0 DEG C by smectic phase, from nematic Phase for it is each to
The temperature of phasic property liquid is 244.0 DEG C.
As shown in figure 5, product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol of embodiment 5
Ester (COON-13) is 115.4 DEG C by the temperature of another crystalline phase of crystallization phase in version, and nematic temperature is changed into by smectic phase
It is that each temperature to phasic property liquid is 187.3 DEG C from nematic Phase for 140.0 DEG C.
As shown in fig. 6, product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- of embodiment 6
Triazol radical phenol ester (COON-123) is 88.4 DEG C by the temperature of another crystalline phase of crystallization phase in version, is changed into smectic phase
Temperature is 126.7 DEG C, and each temperature to phasic property liquid is changed into for 170.7 DEG C from smectic phase.
As shown in fig. 7, product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- of embodiment 7
Triazol radical phenol ester (COON-124) is 94.4 DEG C by the temperature of another crystalline phase of crystallization phase in version, is changed into smectic phase
Temperature is 128.7 DEG C, and each temperature to phasic property liquid is changed into for 155.3 DEG C from smectic phase.
Embodiment 9
Phase research is carried out to the compound of the present invention with petrographic microscope, the transformation behavior occurred in heating and cooling process
It is listed in Table 1 below.Wherein Cr represents crystal, and SmB and SmC represent smectic phase B, C respectively.Iso represents isotropic liquid.
Table 1
Fig. 8 is the product 4- of embodiment 1 [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenylimidazole
(CF2ON-13 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively the compound in 183 DEG C, 231 DEG C of POM
Collection of illustrative plates.
Fig. 9 be embodiment 2 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3 ,-triazole (CF2ON-123 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively that the compound exists
180 DEG C, 234 DEG C of POM collection of illustrative plates.
Figure 10 be embodiment 3 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,4 ,-triazole (CF2ON-124 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively that the compound exists
173 DEG C, 198 DEG C of POM collection of illustrative plates.
Figure 11 be embodiment 4 product 4- [trans- 4- (trans- 4- n-propyls cyclohexyl) cyclohexyl difluoro-methoxy] phenyl-
1H-1,2,3,4- tetrazoles (CF2ON-1234 petrographic microscope collection of illustrative plates (POM collection of illustrative plates))；Wherein, a, b are respectively the compound
In 191 DEG C, 240 DEG C of POM collection of illustrative plates.
Figure 12 is product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) imidazole radicals phenol ester of embodiment 5
(COON-13) petrographic microscope collection of illustrative plates (POM collection of illustrative plates)；Wherein, a, b are respectively that the compound is schemed in 144 DEG C, 179 DEG C of POM
Spectrum.
Figure 13 is the nitrogen of product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,3- three of embodiment 6
The petrographic microscope collection of illustrative plates (POM collection of illustrative plates) of oxazolyl phenol ester (COON-123)；Figure 13 is POM collection of illustrative plates of the compound at 153 DEG C.
Figure 14 is the nitrogen of product 4- (4- (trans- 4- n-propyls cyclohexyl) hexahydrobenzoid acid) -1H-1,2,4- three of embodiment 7
The petrographic microscope collection of illustrative plates (POM collection of illustrative plates) of oxazolyl phenol ester (COON-124)；Figure 14 is POM collection of illustrative plates of the compound at 155 DEG C.
The DSC test results and petrographic microscope characterization result of integrated embodiment 8 can be seen that embodiment 1,2,3,4,5,
6th, 7 product has wide mesomorphic phase temperature range.
The result of phase research is carried out with reference to 1 pair of table compound of the invention, show the present invention using difluoro-methoxy as
The all nematic phases of penta azacyclo liquid-crystal compounds of bridged bond, except compound CF2ON-1234,169 DEG C to 219 DEG C it
Between there is smectic B.Such liquid-crystal compounds has the mesomorphic phase temperature range and high clearing point of non-constant width.For example：
CF2ON-12 (247.5 DEG C of 127.3 DEG C of Cr, N), CF2ON-13 (233.0 DEG C of 124.5 DEG C of Cr, N).
As it can be seen from table 1 with the number increase of compound end N atoms, the fusing point of compound is in increase, nematic phase
Temperature range reduce.Such as：CF2ON-12 fusing point is 127.3 DEG C, CF2ON-123, fusing point be 176.3 DEG C, CF2ON-
1234 fusing point is 169.0 DEG C.This is due to that the polarity that nitrogen-atoms is brought makes the fusing point of compound more high, but end azepine
The addition of ring, extends linear core, obtains larger draw ratio, adds the anisotropy of polarization, therefore containing penta azacyclo
Difluoromethoxy base class liquid-crystal compounds has wide phase transition temperature.And can be to its thing by simply changing end penta azacyclo
Reason and liquid crystal property carry out Effective Regulation.Although the series compound has dystectic problem, still can apply to mixture to
Row phase mixture, is used as the main component of increase nematic phase equilibrium temperature.
Nitrogen-atoms also has a certain impact in the position of five-ring heterocycles to nematic phase, such as CF2ON-12 (127.3 DEG C of Cr,
N247.5 DEG C), CF2ON-13 (233.0 DEG C of 124.5 DEG C of Cr, N), CF2ON-123 (246.0 DEG C of 176.3 DEG C of Cr, N),
CF2ON-124 (241.7 DEG C of 160.6 DEG C of Cr, N), CF2ON-125 (242.5 DEG C of 125.3 DEG C of Cr, N).
There is smectic B or smectic C phases in penta azacyclo liquid-crystal compounds part by bridged bond of ester group.Although in ladder
The ester group of shape maintains the linear structure of molecule to a certain extent, but contrasts difluoro-methoxy, which increases the width of molecule
Degree, which results in the reduction of the appearance of smectic phase, and nematic phase member temperature range.
Embodiment 10
The liquid-crystal compounds containing penta azacyclo by bridged bond of difluoro-methoxy is dissolved in eight with the ratio of 10% or 5%
In the commercialization nematic phase mixed crystal 1C40300-000 that hundred million space-time liquid crystal material Co., Ltds produce, drawn with calculation by extrapolation
Compound and dielectric constant, refractive index, viscosity.As shown in table 2.
Table 2
Wherein A1 structure and physical property are as follows：
As shown in table 2, the CF of liquid-crystal compounds containing penta azacyclo2ON-12 has minimum viscosity, CF2ON-13 has most
High dielectric constant, CF2ON-125 has highest refractive index.Compound CF in the present invention2ON-12、CF2ON-13、
CF2ON-123、CF2ON-124、CF2ON-125 nematic temperature range is wider than commercialized liquid-crystal compounds A1, is conducive to
Expand the temperature applicable range of mixed crystal, their birefringence Δ n is also higher than A1.Compound CF2ON-12、CF2ON-13、
CF2ON-124 viscosity is lower than A1, when being added in mixed crystal, advantageously reduces the response time of liquid crystal display.
Comprehensive properties, the penta azacyclo liquid-crystal compounds containing difluoro-methoxy has the physics and liquid crystal liquid crystal property of uniqueness
Matter, such as non-constant width nematic temperature range, can be used as liquid crystal display material；High clearing point, wide warm, high dielectric can also be used as
The liquid crystal components of constant, are added to regulation performance in mixed crystal.This explanation uses penta azacyclo simple and easy to get for end group
These obtained liquid-crystal compounds not only have cost relatively low, synthesize simple and convenient, high income, and by simply changing end
Azacyclo- can carry out Effective Regulation to physics and liquid crystal property.
Meanwhile, multiple nitrogen-atoms are contained in penta azacyclo liquid-crystal compounds end, can be expected to metal formation complex
Develop into fluorescent liquid crystal material.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of liquid-crystal compounds containing penta azacyclo, it is characterised in that with structure as shown in Equation 1：
Wherein, Y is CF2O, n are 3 or 5, m are 1 or 2；
R1、R2、R3、R4For H or F.
2. the liquid-crystal compounds according to claim 1 containing penta azacyclo, it is characterised in that：N is 3.
3. the liquid-crystal compounds according to claim 1 containing penta azacyclo, it is characterised in that：R1=R2=R3=R4=H.
4. the liquid-crystal compounds according to claim 1 containing penta azacyclo, it is characterised in that：For
5. the liquid-crystal compounds according to claim 1 containing penta azacyclo, it is characterised in that：Described contains five yuan of azepines
The liquid-crystal compounds of ring is one kind in following structure：
6. the intermediate obtained during any one of the synthesis claim 1-5 compound, its structure is as follows：
7. when Y is CF2During O, the synthetic method of the liquid-crystal compounds containing penta azacyclo described in claim any one of 1-5, its
It is characterised by comprising the following steps：
(1) two sulfosalts shown in formula 2 are dissolved in dichloromethane, are cooled to -70 DEG C, then the compound shown in formula 3a is slowly added dropwise
And Et3N dichloromethane solution, stirs and Et is added in 1h, 15min3N-3HF, is added containing Br2CH2Cl2Solution；Naturally rise
Temperature obtains the product shown in formula 4a after completion of the reaction to 0 DEG C；
The compound shown in two sulfosalts, formula 3a shown in formula 2, Et3N、Et3N-3HF and Br2Mol ratio be 1:(1-2):(1-
2):(3-5):(3-5)；
(2) by the compound shown in formula 4a, penta azacyclo, CuI, Cs2CO3It is dissolved in dimethylformamide, is heated to 120 DEG C
24h is reacted, the liquid-crystal compounds shown in formula 5a is obtained after completion of the reaction；
Compound, penta azacyclo, CuI and Cs shown in formula 4a2CO3Mol ratio be 1:(1-2):(0.2-0.4):(1-2)；
In formula 2, n is 3 or 5；M is 1 or 2；
In formula 3a, R1、R2、R3、R4For H or F；
Described penta azacyclo is
8. when Y is CF2O、During for tetrazole ring, claim 1-3 and the liquid containing penta azacyclo described in 5 any one
The synthetic method of crystallization compound, it is characterised in that comprise the following steps：
(1) two sulfosalts shown in formula 2 are dissolved in dichloromethane, are cooled to -70 DEG C, then the compound shown in formula 3a is slowly added dropwise
And Et3N dichloromethane solution, stirs and Et is added in 1h, 15min3N-3HF, is added containing Br2CH2Cl2Solution；Naturally rise
Temperature obtains the product as shown in formula 4b after completion of the reaction to 0 DEG C；
The compound shown in two sulfosalts, formula 3b shown in formula 2, Et3N、Et3N-3HF and Br2Mol ratio be 1:(1-2):(1-
2):(3-5):(3-5)；
(2) by the compound shown in formula 4b, NH4Cl is dissolved in the mixed solution of methanol and tetrahydrofuran, adds zinc powder, and room temperature is stirred
24h is mixed, the product shown in formula 5b is obtained after completion of the reaction；
Compound, Zn and NH shown in formula 4b4Cl mol ratio is 1:(4-6):(4-6)；
(3) compound shown in formula 5b, triethyl orthoformate, sodium azide are placed in tube sealing, are rapidly added under fume hood
Acetic acid, is warming up to 80 DEG C of reaction 4h, the liquid-crystal compounds as shown in formula 6b is obtained after completion of the reaction；
The mol ratio of compound, triethyl orthoformate and sodium azide shown in formula 5b is 1:(2-3):(1-1.5)；
In formula 2, n is 3 or 5；M is 1 or 2；
In formula 3b, R1、R2、R3、R4For H or F.
9. application of the liquid-crystal compounds containing penta azacyclo described in claim any one of 1-5 in liquid crystal display material.
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