CN101565343B - Preparation method of difluoro methoxy bridge bond compound - Google Patents
Preparation method of difluoro methoxy bridge bond compound Download PDFInfo
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- CN101565343B CN101565343B CN 200910098545 CN200910098545A CN101565343B CN 101565343 B CN101565343 B CN 101565343B CN 200910098545 CN200910098545 CN 200910098545 CN 200910098545 A CN200910098545 A CN 200910098545A CN 101565343 B CN101565343 B CN 101565343B
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Abstract
The invention discloses a preparation method for inducing difluoro methoxy central bridge bonds (CF2O) in the molecules of a compound by 'one-pot method'. Organic acid is used to obtain trifluoromethane sulphonate under the action of dimercaptopropane-trifluoromethane sulfoacid, and at low temperature, phenol or various fortified phenols, pyridine fluorine hydride and bromine are directly added to prepare the difluoro methoxy central bridge bonds compound without separation. The synthetic method is simple and highly efficient and especially applicable to the synthesis of a liquid crystal compound with the difluoro methoxy central bridge bonds (CF2O).
Description
Technical field
The present invention relates in compound molecule, introduce difluoro methoxy bridge bond (CF
2O) synthetic method, particularly difluoro methoxy bridge bond (CF
2O) liquid crystalline cpd preparation method.
Background technology
Along with tft liquid crystal shows the development of (TFT-LCD) technology and people to the improving constantly of display requirement, more and more higher to the quality requirements of liquid-crystal display.Its developing direction is to realize quick response, reduces driving voltage to reduce power consumption etc.And liquid crystal material is one of crucial photoelectron material of liquid-crystal display, and it gives the LCD device various good performances.In order to satisfy the requirement of liquid crystal display device development, the requirement of the viscosity of reduction mixed liquid crystal and increase dielectric anisotropy is urgent, therefore requires to develop high polarity, low viscous monomer liquid crystal and synthetic method.
At present, having high dielectric anisotropy and low viscous monomer liquid crystal mainly is the monomer liquid crystal compound that contains difluoro-methoxy center bridged bond, and this compound liquid crystal is widely used in the TFT-LCD mixed liquid crystal.Because contain the monomer liquid crystal compound complicated process of preparation of difluoro-methoxy center bridged bond, price is high, the industrialization difficulty.Therefore developing simple, easy industrialized synthetic method has great importance to cost, the realization suitability for industrialized production that reduces liquid crystal material.
Have high dielectric anisotropy, and the monomer liquid crystal compound of widely used difluoro-methoxy center bridged bond have following general formula:
(F) the expression fluorine atom exists or does not exist, and R is alkyl
The synthetic difficult point of formula II liquid crystalline cpd is how to introduce easily difluoro-methoxy center bridged bond (CF in molecule
2O), at present, the synthetic method of bibliographical information is mainly by following three kinds.
● the dibromodifluoromethane method
Utilize the reaction of the grignard reagent of alkyl or phenyl or lithium reagent and dibromodifluoromethane, obtain alkyl or phenyl difluoro monobromethane, again and fortified phenol effect under etherificate, thereby in liquid crystal molecule, introduce difluoro methoxy center bridged bond (CF
2O).
The method subject matter is that the source of dibromodifluoromethane is rare, and is lower to the yield of polycyclic system reaction, causes cost higher.
● the DAST method
Various esters (COO) and Lawesson reagent react are generated monothioester, be that DAST reacts at low temperatures, thereby ester group is converted into difluoro methoxy center bridged bond (CF
2O)
The method subject matter is the price is rather stiff of DAST, and yield is lower, causes the preparation cost of compound higher.
● dimercaptopropane-trifluoromethayl sulfonic acid method
The method divided for two steps: 1) alkyl or phenyl formic acid and dimercaptopropane and trifluoromethayl sulfonic acid reaction, and the preparation trifluoro-methanyl sulfonate, through separating, recrystallization obtains purity greater than 96% salt.2) this salt at low temperatures through and phenol, pyridine hydrogen fluoride and bromine reaction, obtain difluoro methoxy center bridged bond (CF
2O) compound.
The method subject matter is that minute two steps are synthetic, and the purification loss of trifluoro-methanyl sulfonate is larger, and low-melting salt recrystallization difficulty causes overall yield lower, and the preparation cost of compound is higher.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of difluoro methoxy bridge bond compound, and it adopts dimercaptopropane-trifluoromethayl sulfonic acid " one kettle way " preparation method, introduces difluoro methoxy center bridged bond (CF in compound molecule
2O).For this reason, the present invention is by the following technical solutions: it adopts following steps:
Organic acid obtains trifluoro-methanyl sulfonate under dimercaptopropane-trifluoromethayl sulfonic acid effect, without separation, at low temperatures, directly add phenol or various fortified phenol, pyridine hydrogen fluoride and bromine, thus preparation difluoro methoxy center bridged bond compounds.Its reaction expression is suc as formula shown in the I.
(formula I)
Organic acid shown in the formula I is alkyl formate, substituted cyclohexyl formic acid or substituted benzoic acid etc.
Phenol shown in the formula I is the phenol of various replacements, such as the various fluorophenols etc. that contain.
If for the preparation of liquid crystalline cpd, then R is:
R
1Be selected from the alkyl of C1-C15, (F) the expression fluorine atom exists or does not exist.
If for the preparation of liquid crystalline cpd, described fortified phenol is selected from: 4-fluorophenol, 3, the 4-difluorophenol, 3,4,5-trifluoromethyl phenol, 4-trifluoro-methoxy-phenol, 3-fluoro-4-trifluoro-methoxy-phenol, 3,5-two fluoro-4-trifluoro-methoxy-phenols, 4-trifloro methyl phenol, 3-fluoro-4-trifloro methyl phenol, 3,5-two fluoro-4-trifloro methyl phenols.
Concrete preparation method provided by the invention is that various organic acids mix with dimercaptopropane-trifluoromethayl sulfonic acid, adds solvent toluene or toluene and octane-iso mixed system, and reflux is utilized the water trap dehydration, until anhydrous separating out.After the cooling, add methylene dichloride or ethylene dichloride, utilize after liquid nitrogen-ethanol or liquid nitrogen-the acetone system is cooled to low temperature, add phenol or various fortified phenol, pyridine hydrogen fluoride and bromine, react complete, carry out aftertreatment and obtain difluoro methoxy center bridged bond compounds.
In the aforesaid method, the molar ratio of various organic acids and dimercaptopropane-trifluoromethayl sulfonic acid is 1: 1～2.5: 1～2.5; Organic acid and solvent toluene or toluene and octane-iso mixed system ratio are 1mol: 100ml～1000ml, and wherein, the volume ratio of toluene or toluene and octane-iso is 1: 1; The reflux temperature is 100～120 ℃; The time of dehydration reaction is 3～36 hours; Organic acid and methylene dichloride or ethylene dichloride ratio are 1mol: 100ml～1000ml; Utilize after liquid nitrogen-ethanol or liquid nitrogen-the acetone system is cooled to low temperature, temperature range is-90～-60 ℃; The molar ratio of organic acid and phenol or various fortified phenols is 1: 0.8～2; The hydrofluoric molar ratio of organic acid and pyridine is 1: 0.5～5, and the molar ratio of organic acid and bromine is 1: 0.5～5.Pass through NaHCO
3The aqueous solution makes system be weakly alkaline, after telling organic phase and processing, and is stationary phase with silica gel, and sherwood oil or normal hexane are moving phase, the post separation, and recrystallization obtains containing the target compound of difluoro methoxy bridge bond.
" one kettle way " synthetic method of difluoro methoxy bridge bond compound provided by the invention, be mainly used in and in compound molecule, introduce difluoro methoxy bridge bond, the preparation method is simple, particularly be applied to the synthetic of high dielectric anisotropic liquid crystal compound, with the yield that improves reaction and the quality of product, the preparation of high polarity, low viscosity liquid crystal material is had great importance.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and embodiment is synthetic mainly for liquid crystalline cpd, but the present invention is not limited to the synthetic of liquid crystalline cpd, can be applied to all and introduce the synthetic of difluoro methoxy bridge bond compound.
Embodiment 1,
In the 2L there-necked flask, add trans, trans-propyl group dicyclohexyl formic acid (126g, 0.5mol), 150ml toluene, 150ml octane-iso and (65g, 0.6mol) 1, the 3-dimercaptopropane is when being warming up to 45 ℃, drip (89.5g, 0.6mol) trifluoromethanesulfonic acid, slowly be heated to backflow, utilize the water trap dehydration, 6 hours reaction times, complete, be cooled to room temperature, add the 100ml methylene dichloride.Install under liquid nitrogen-acetone cold cooling unit and the nitrogen protection; be cooled to-70 ℃; drip the 50ml methylene dichloride; (74g; 0.5mol) 3,4, the 5-trifluoromethyl phenol; (56g; 0.55mol) triethylamine, dropwise, stirred 1.5 hours below-70 ℃; add rapidly 242ml (1.5mol) HFPy in the time of again-70 ℃; then dripped the 30ml dichloromethane solution of 240g (1.5m mol) bromine in 1.5 hours, finished in 30 minutes ,-70 ℃ were stirred 1 hour; when naturally being warming up to 0 ℃, be poured into 168g (2mol) NaHCO
3In the mixture of the aqueous solution (500ml) and 300g ice, make to be weakly alkaline, tell organic phase, extract secondary with 500ml*2, merge organic phase, use 5%NaHSO
3The aqueous solution (50ml) washing 1 time, deionized water wash 2 times is to neutral.Na
2SO
4Drying, decompression steams solvent, and take silica gel as stationary phase, sherwood oil is that moving phase is carried out the post separation, steams sherwood oil.Use the sherwood oil recrystallization, suction strainer gets 165.5g, yield 82%, gas chromatographic purity 99.5%.
Embodiment 2,
With embodiment 1, just add (86.5g, 0.8mol) 1,3-dimercaptopropane and dropping (120g, 0.8mol) trifluoromethanesulfonic acid obtain target compound 169.5g, yield 84%, gas chromatographic purity 99.5%.
Embodiment 3,
With embodiment 1, be that freezing low temperature obtains target compound 169.5g to-75 ℃ ,-80 ℃ and-85 ℃ respectively, yield is respectively 82%, 85% and 82%, gas chromatographic purity 99.5%.
Embodiment 4,
With embodiment 1, just add respectively 67g (0.45mol) and 89g (0.6mol) phenol, yield is respectively 78% and 83%, gas chromatographic purity 99.5%.
Embodiment 5,
With embodiment 1, just add respectively 161ml (1mol) HFPy, and the 100ml dichloromethane solution of 160g (1mol) bromine; Just add respectively 483ml (3mol) HFPy, and the 100ml dichloromethane solution yield of 480g (3mol) bromine is respectively 74% and 82%, gas chromatographic purity 99.5%.
Embodiment 6,
In the 2L there-necked flask, add trans-propyl cyclohexyl formic acid (123g, 0.5mol), 150ml toluene, 150ml octane-iso and (65g, 0.6mol) 1, the 3-dimercaptopropane when being warming up to 45 ℃, drips (89.5g, 0.6mol) trifluoromethanesulfonic acid, slowly be heated to backflow, utilize the water trap dehydration, 4 hours reaction times, complete, be cooled to room temperature, add the 100ml methylene dichloride.Install under liquid nitrogen-acetone cold cooling unit and the nitrogen protection, be cooled to-75 ℃, drip the 50ml methylene dichloride; (74g; 0.5mol) 3,4, the 5-trifluoromethyl phenol; (56g; 0.55mol) triethylamine, dripped, stirred 1.5 hours below-75 ℃; add rapidly 242ml (1.5mol) HFPy in the time of again-70 ℃, then in 1.5 hours, drip 240g (1.5m
Mol) the 30ml dichloromethane solution of bromine finished in 30 minutes, and-75 ℃ were stirred 1 hour, and when naturally being warming up to 0 ℃, were poured into 168g (2mol) NaHCO
3In the mixture of the aqueous solution (500ml) and 300g ice, make to be weakly alkaline, tell organic phase, extract secondary with 500ml*2, merge organic phase, use 5%NaHSO
3The aqueous solution (50ml) washing 1 time, deionized water wash 2 times is to neutral.Na
2SO
4Drying, decompression steams solvent, and take silica gel as stationary phase, sherwood oil is that moving phase is carried out the post separation, steams sherwood oil.Use the sherwood oil recrystallization, suction strainer gets 167g, yield 84%, gas chromatographic purity 99.5%.
Embodiment 7
With embodiment 6, just 138g (0.5mol) 2 is changed in reactant acid, 6-two fluoro-4-(4-propyl group phenyl) phenylformic acid, and dewatering time is 8 hours, gets target product 182g, yield 85%, gas chromatographic purity 99.5%.
Embodiment 8
With embodiment 6, just 185g (0.5mol) 2 is changed in reactant acid, 6-two fluoro-4-[2 '-fluoro-4 '-(4 ' '-the propyl group phenyl) phenyl]-phenylformic acid, dewatering time is 16 hours, get target product 188g, yield 72%, gas chromatographic purity 99.5%.
Embodiment 9
With embodiment 6, just reactant phenol is changed into 67g (0.6mol) 4-fluorophenol, gets target product 163g, yield 86%, gas chromatographic purity 99.5%.
Embodiment 10
With embodiment 6, just reactant phenol is changed into 78g (0.6mol) 3, and the 4-difluorophenol gets target product 163g, yield 86%, gas chromatographic purity 99.5%.
Embodiment 11
With embodiment 6, just reactant phenol is changed into 107g (0.6mol) 4-trifluoro-methoxy-phenol, gets target product 154g, yield 72%, gas chromatographic purity 99.5%.
Embodiment 11
With embodiment 6, just reactant phenol is changed into 117.5g (0.6mol) 3-fluoro-4-trifluoro-methoxy-phenol, gets target product 154g, yield 72%, gas chromatographic purity 99.5%.
Claims (2)
1. preparation method of difluoro methoxy bridge bond compound is characterized in that:
Organic acid mixes with dimercaptopropane-trifluoromethayl sulfonic acid, adds solvent toluene or toluene and octane-iso mixed system, and reflux is utilized the water trap dehydration, until anhydrous separating out; After the cooling, add methylene dichloride or ethylene dichloride, utilizing liquid nitrogen-ethanol or liquid nitrogen-acetone system to be cooled to temperature range is behind-90～-60 ℃ the low temperature, add phenol or fortified phenol, pyridine hydrogen fluoride and bromine, react complete, carry out aftertreatment and obtain difluoro methoxy bridge bond compound
The organic acid structural formula is R-COOH,
Phenol or fortified phenol are
Wherein select X definition so that
Be phenol or fortified phenol, and fortified phenol is selected from: 4-fluorophenol, 3, the 4-difluorophenol, 3,4,5-trifluoromethyl phenol, 4-trifluoro-methoxy-phenol, 3-fluoro-4-trifluoro-methoxy-phenol, 3,5-two fluoro-4-trifluoro-methoxy-phenols, 4-trifloro methyl phenol, 3-fluoro-4-trifloro methyl phenol, 3,5-two fluoro-4-trifloro methyl phenols
The structure of difluoro methoxy bridge bond compound is
In the difluoro methoxy bridge bond compound definition of X with
The definition of middle X is identical,
R is:
R
1Be selected from the alkyl of C1-C15, (F) the expression fluorine atom exists or does not exist.
2. preparation method of difluoro methoxy bridge bond compound according to claim 1, it is characterized in that: the molar ratio of organic acid and dimercaptopropane-trifluoromethayl sulfonic acid is 1: 1～2.5: 1～2.5; Organic acid and solvent toluene or toluene and octane-iso mixed system ratio are 1mol: 100ml～1000ml, wherein, and the volume ratio of toluene and octane-iso 1: 1; The reflux temperature is 100～120 ℃; The time of dehydration reaction is 3～36 hours; Organic acid and methylene dichloride or ethylene dichloride ratio are 1mol: 100ml～1000ml; Utilize after liquid nitrogen-ethanol or liquid nitrogen-the acetone system is cooled to low temperature, temperature range is-90～-60 ℃; The molar ratio of organic acid and phenol or various fortified phenols is 1: 0.8～2; The hydrofluoric molar ratio of organic acid and pyridine is 1: 0.5～5, and the molar ratio of organic acid and bromine is 1: 0.5～5.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358662A (en) * | 1992-05-28 | 1994-10-25 | Chisso Corporation | Liquid crystal composition and a liquid crystal display element using the same |
| CN1827580A (en) * | 2005-02-28 | 2006-09-06 | 大丰市天生药业有限公司 | Process for synthesis of 3-difluoro methoxy -2,4,5-trifluoro benzoic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358662A (en) * | 1992-05-28 | 1994-10-25 | Chisso Corporation | Liquid crystal composition and a liquid crystal display element using the same |
| CN1827580A (en) * | 2005-02-28 | 2006-09-06 | 大丰市天生药业有限公司 | Process for synthesis of 3-difluoro methoxy -2,4,5-trifluoro benzoic acid |
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