CN105481662A - Method for preparing intermediate for producing difluoromethoxy containing liquid crystal compound - Google Patents
Method for preparing intermediate for producing difluoromethoxy containing liquid crystal compound Download PDFInfo
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Abstract
The invention discloses a method for preparing an intermediate compound represented by a formula A shown in the description for producing a difluoromethoxy containing liquid crystal compound. The compound A is prepared by taking 3,4,5-trifluorophenol as an initial raw material. According to the method, the operation is simple and convenient, the cost is low, and the yield is high, so that the method is applicable to industrial production.
Description
Technical field
The present invention relates to field of liquid crystals, be specifically related to a kind of method and this midbody compound for the preparation of producing the intermediate containing difluoro-methoxy liquid crystalline cpd and preparing the application in liquid crystalline cpd.
Background technology
Since 1988 find liquid crystal, be with a wide range of applications because liquid crystal has the character of many uniquenesses.Such as, in chemical industry, liquid crystal can as orderly solvent, promotes organic chemistry orientation response, and stereoisomerism is selected, optical rotatory substance enrichment be separated, chromatogram selectivity and separation efficiency can be improved as Stationary liquids; Liquid crystal state functional membrane has the best separation efficiency of selective penetrating quality.In the electronics industry, liquid crystal owing to having the incomparable superior character of many other materials, as: power consumption is extremely low, driving voltage is low, fast response time, shows under bright light environments, thus obtains in electronic display technology and microtronics and apply more and more widely.Just because of above-mentioned successful application and development, people are impelled to synthesize the liquid crystalline cpd different with studying up to ten thousand kinds.
Recent two decades comes, and liquid crystal material, due to the photoelectric properties of its uniqueness, is widely used in industry and daily life.As a kind of novel display material, it not only has that power consumption is extremely low, driving voltage is low, fast response time, the particular advantages that shows under bright light environments, also have size flexibly, panelized, meandering, the feature such as display is clear, applied widely, cost is low.Therefore, along with people are more and more higher to liquid-crystal display quality requirements, in order to meet the requirement of liquid crystal display device development, the viscosity reducing mixed liquid crystal is very urgent with the requirement increasing dielectric anisotropy, therefore requires exploitation high polarity, low viscous monomer liquid crystal and synthetic method thereof.
At present, there is high dielectric anisotropy and the monomer liquid crystal compound of low viscous monomer liquid crystal mainly containing difluoro-methoxy, there is this liquid crystalline cpd and be widely used in TFT-LCD mixed liquid crystal.There is the liquid crystalline cpd of difluoro-methoxy, because Stability Analysis of Structures causes its electric charge conservation rate high; Moment of dipole strengthens, and causes its dielectric anisotropy comparatively large, is conducive to the reduction of saturation voltage; Replace ester bond to cause the viscosity of mixed liquid crystal to reduce with difluoro-methoxy, be conducive to the raising of response speed.In liquid crystal molecule skeleton, introduce difluoro-methoxy have a variety of method, in different document, have multiple telling about.
CN1628165A discloses compd A
A kind of preparation method, the method is with 3,5, and-difluoro bromobenzene is raw material, prepares compd A through a series of reaction.The process employs the expensive and sulphur reagent that toxicity is large, productive rate is low and reaction is complicated, is not suitable for scale operation.
As the key intermediate of preparation containing difluoro-methoxy liquid crystalline cpd, it is existing open in CN1628165A and CN102477305A that compd A is used to prepare liquid crystalline cpd.
In order to solve problems of the prior art, the invention provides a kind of method for the preparation of compd A newly, described compd A can as intermediate for the preparation of the monomer liquid crystal compound containing difluoro-methoxy.Described method is with 3,4, the 5-trifluoromethyl phenols be cheaply easy to get for raw material, and the intermediate often walking reaction is all easy to purify, and yield is higher, is applicable to suitability for industrialized production.
Summary of the invention
The object of the invention is to for above shortcomings in prior art provide a kind of for the preparation of compd A be easy to purify, yield is higher, reduce the new preparation method of actual production operation easier and cost.Described compd A can be used as intermediate, in order to the liquid crystalline cpd of preparation containing difluoro-methoxy.
One aspect of the invention provides the preparation method of compd A, comprises following 4 steps successively:
Particularly, the invention provides a kind of method preparing compd A, said method comprising the steps of:
1) by compound 1
Under the alkaline condition that there is alkaline reagents, and ethyl bromide difluoride or difluoro methyl bromoacetate reaction, obtain the compound of formula 2
Wherein R represents CH
3or C
2h
5;
2) by the compound of described formula 2 under the alkaline condition that there is alkaline reagents, be hydrolyzed reaction, obtains compound 3
3) described compound 3 is carried out bromination reaction, obtain compound 4
4) by described compound 4 and the fluoro-2-iodobenzene of the bromo-13-of 5-
Under the existence of transition metal, be obtained by reacting compd A, described transition metal is selected from the group be made up of copper and zinc.
In preparation method of the present invention, described step 3) in the preparation method of compound 4 be following method i) or method ii) in any one:
I) by described compound 3 and red precipitate and bromide reagent back flow reaction in a solvent, after completion of the reaction through aftertreatment, compound 4 is obtained; Or
Ii) by described compound 3 and plumbic acetate and bromide reagent back flow reaction in a solvent, after completion of the reaction through aftertreatment, described compound 4 is obtained.
In preparation method of the present invention, described step 4) in compd A preparation method be following method i):
I) described compound 4, bromo-1, the 3-fluoro-2-iodobenzene of 5-and copper powder are added in solvent react, after completion of the reaction through aftertreatment, obtain described compd A.
In preparation method of the present invention, described step 4) in compd A preparation method be following method ii):
Ii) described compound 4 and zinc powder are added in solvent react, then add bromo-1, the 3-fluoro-2-iodobenzene of palladium catalyst, part and 5-, continue reaction, after completion of the reaction through aftertreatment, obtain described compd A.
In preparation method of the present invention, described step 1) temperature of reaction be 50 ~ 120 DEG C, the reaction times is 1 ~ 10h, and preferable reaction temperature is 60 ~ 100 DEG C, and the reaction times is 2 ~ 6h.
In preparation method of the present invention, described step 2) temperature of reaction be 15 ~ 60 DEG C, the reaction times is 1 ~ 10h, and preferable reaction temperature is 20 ~ 40 DEG C, and the reaction times is 1 ~ 5h.
In preparation method of the present invention, described step 3) temperature of reaction be 25 ~ 62 DEG C, the reaction times is 1 ~ 10h, and preferable reaction temperature is 40 ~ 62 DEG C, and the reaction times is 1 ~ 5h.
In preparation method of the present invention, described step 4) temperature of reaction be 25 ~ 120 DEG C, the reaction times is 3 ~ 30h, and preferable reaction temperature is 25 ~ 80 DEG C, and the reaction times is 5 ~ 24h.
In preparation method of the present invention, described step 1), 2), 3) and 4) carry out all in the presence of an organic, described step 1), 2), 3) and 4) in described organic solvent be selected from independently of one another by C
1-C
4lower alcohol, methylene dichloride, methyl-sulphoxide, trifluoroacetic acid, ethyl acetate, DMF, tetrahydrofuran (THF), chloroform and combination composition group.
In preparation method of the present invention, described step 1) and 2) described in alkaline reagents be selected from the group be made up of sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, salt of wormwood, sodium carbonate, potassiumiodide, sodium bicarbonate, a hydronium(ion) Lithium Oxide 98min, diisopropyl ethylenediamine, triethylamine and combination thereof.
In preparation method of the present invention, described step 3) described in bromide reagent be selected from the group be made up of bromine, N-bromosuccinimide, C5H6Br2N2O2, lithiumbromide, Sodium Bromide, Potassium Bromide and combination thereof.
In preparation method of the present invention, described step 4) described in palladium catalyst be selected from by palladium, tetrakis triphenylphosphine palladium, Palladous chloride, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride, 1, two (diphenyl phosphine) ferrocene palladium chloride (II) chloride dichloromethane complex of 1'-, two (tricyclohexyl phosphine) palladium chloride, two (triphenylphosphine) palladium chloride (II), two (dibenzalacetone) palladium (0), three (dibenzalacetone) two palladium chloroform adducts, two (methyl ethyl diketone) palladium (II), palladium hydroxide charcoal, palladium carbon, (1, 5-cyclooctadiene) palladium chloride, two (acetonitrile) palladium chloride (II), the group of two (cyanophenyl) palladium chloride (II) and combination composition thereof.
In some embodiments, preferred described palladium catalyst is selected from by tetrakis triphenylphosphine palladium, Palladous chloride, palladium, two (dibenzyl subunit acetone) palladium and the group that forms thereof.
In preparation method of the present invention, described step 4) in part be selected from by triphenylphosphine, tricyclohexyl phosphine, diphenylcyclohexyl phosphine, 4, the two diphenylphosphine-9 of 5-, 9-dimethyl xanthene, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 2-dicyclohexyl phosphine-2', 6'-dimethoxy-biphenyl, di-t-butyl cyclohexyl phosphine, three (o-tolyl) phosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 6'-diisopropoxy-1, 1'-biphenyl, Q-Phos, 1, two (diphenylphosphine) ferrocene of 1'-, 2-di-t-butyl phosphine-2', 4', the group of 6'-tri isopropyl biphenyl and combination composition thereof.
In some embodiments, preferred described part is selected from by 2-dicyclohexylphosphontetrafluoroborate-2', 6'-diisopropoxy-1,1'-biphenyl, Q-Phos, 1,1'-two (diphenylphosphine) ferrocene, 2-di-t-butyl phosphine-2', the group of 4', 6'-tri isopropyl biphenyl and combination composition thereof.
Compd A of the present invention can be used as Intermediate Preparation containing difluoro-methoxy liquid crystalline cpd.
The invention has the advantages that: the method has following advantage:
1. the supplementary material needed for is commercially available industrial chemicals, and buying cost is low, thus reduces production cost;
2. purity is high, and yield is good;
3. reaction conditions is gentle, and simple to operate, be suitable for suitability for industrialized production;
4. overcome the taste that exists in prior art and the large defect of toxicity, reduce danger.
Therefore, adopt preparation method of the present invention greatly can reduce implementation cost, be conducive to realizing suitability for industrialized production, there is high industrial application value.
It will be understood by those skilled in the art that above-mentioned reaction conditions, comprise the reaction conditions of aforesaid synthetic compound A, is not the sole mode realizing technical solution of the present invention.Those skilled in the art can not depart from the basis of present inventive concept, change and realize technical scheme of the present invention according to actual needs to described reaction conditions.
Accompanying drawing explanation
Fig. 1 is the MS figure of compound 2;
Fig. 2 is compound 3
1h-NMR schemes;
Fig. 3 is the MS figure of compound 4;
Fig. 4 is the MS figure of compd A;
Fig. 5 is the MS figure of compound 6; And
Fig. 6 is the MS figure of compound 8.
Embodiment
Below with reference to specific embodiments, the present invention is described.It should be noted that, the following examples are example of the present invention, are only used for the present invention is described, and are not used for limiting the present invention.
In following examples, except compd A, compound 2, compound 3 and compound 4, all the other compound monomers used and related reagent all can be buied from market.Wherein,
reagent name be 3,4,5-trifluoromethyl phenol, No. CAS is 99627-05-1,
reagent name be bromo-1, the 3-fluoro-2-iodobenzene of 5-, No. CAS is 160976-02-3.
Embodiment 1
1) preparation of compound 2
Taking 14.8g compound 1 joins in 80mL tetrahydrofuran (THF), adds sodium hydride (60%, 4.4g) under room temperature in batches, adds rear stirring 1h, disposablely adds 21g ethyl bromide difluoride, is warmed up to 80 DEG C, reaction 3h.Add 100mL water, 200mL*3 extraction into ethyl acetate aqueous phase, dry, be spin-dried for.Add 40g100 ~ 200 object silica gel mixed sample, pad 200 ~ 300 order silica gel of 3 times, the sherwood oil of 50:1 and the mixed solvent 1L of ethyl acetate rinse post, obtain 25g yellow solid (compound 2).GC:99.2%, yield: 92%.
The MS figure of compound 2 is see Fig. 1.
2) preparation of compound 3
Take 25g compound 2 and 8g mono-hydronium(ion) Lithium Oxide 98min, be dissolved in the mixed solvent of 80mL methyl alcohol and 50mL water, 25 DEG C of reaction 3h, use 300mL extraction into ethyl acetate, dry, are spin-dried for, obtain 22g white solid (compound 3), yield: 98%.
1H-NMR(d
6-DMSO)δ：8.466(d,1H)；8.132(s,1H)。
Compound 3
1h-NMR figure is see Fig. 2.
3) preparation of compound 4
Taking 22g compound 3 is dissolved in 100mL chloroform, adds 23g red precipitate at 40 DEG C, then slowly drips 32g bromine, back flow reaction 4h, and cooling is filtered, added 100mL water, 200mL*3 extraction into ethyl acetate, dry, is spin-dried for, obtains 10g compound 4.GC:99.2%, yield: 41%.
The MS figure of compound 4 is see Fig. 3.
4) preparation of compd A
Take bromo-1, the 3-fluoro-2-iodobenzene of 18g compound 4,21g5-, 25g copper powder is added in 250mL methyl-sulphoxide, 80 DEG C of reaction 24h, reacted and added 300mL water, 3*300mL extraction into ethyl acetate, 100mL*3 washes ethyl acetate, drying, is spin-dried for, and obtains 22g compd A.GC:99.2%, yield: 88%.
The MS figure of compd A is see Fig. 4.
Embodiment 2
1) preparation of compound 4
The compound 3 taking 22g embodiment 1 synthesis is dissolved in 100mL chloroform, adds 25g plumbic acetate, then add 20g lithiumbromide, back flow reaction 4h in batches at 40 DEG C, cooling, filters, adds 100mL water, 200mL*3 extraction into ethyl acetate, drying, is spin-dried for, and obtains 9g compound 4.GC:99.2%, yield: 38%.
2) preparation of compd A
Take 18g compound 4,8.5g zinc powder is added to 150mLN, in dinethylformamide, 25 DEG C are reacted half an hour.Then 0.5g palladium is added, two (diphenylphosphine) ferrocene of 1g1,1'-and bromo-1, the 3-fluoro-2-iodobenzene of 21g5-, 40 DEG C of reaction 5h, reacted and added 300mL water, 3*300mL extraction into ethyl acetate, 100mL*3 washes ethyl acetate, drying, is spin-dried for, and obtains 22g compd A.GC:99.2%, yield: 88%.
Embodiment 3
Take 18g compound 5,21g compd A, 16g salt of wormwood, 0.7g4-(3-Phenylphosphine palladium) is added in the mixed solvent of 150mL toluene, 50mL ethanol and 50mL water, back flow reaction 2h, has reacted and has added 100mL water, 3*300mL extraction into ethyl acetate, 100mL*3 washes ethyl acetate, drying, is spin-dried for, and adds 40g200 ~ 300 object silica gel, thick post excessively, be spin-dried for, obtain 25g compound 6 (known liquid crystalline cpd, see CN102477305A), GC:99.2%, yield: 92%.
The MS figure of compound 6 is see Fig. 5.
Embodiment 4
Take 18g compound 7,21g compd A, 16g salt of wormwood, 0.7g4-(3-Phenylphosphine palladium) is added in the mixed solvent of 150mL toluene, 50mL ethanol and 50mL water, back flow reaction 2h, has reacted and has added 100mL water, 3*300mL extraction into ethyl acetate, 100mL*3 washes ethyl acetate, drying, is spin-dried for, and adds 40g200 ~ 300 object silica gel, thick post excessively, be spin-dried for, obtain 25g compound 8 (known liquid crystalline cpd, see CN102477305A), GC:99.3%, yield: 92%.
The MS figure of compound 8 is see Fig. 6.
Claims (10)
1. prepare the method for compd A for one kind
Said method comprising the steps of:
1) by compound 1
Under the alkaline condition that there is alkaline reagents, and ethyl bromide difluoride or difluoro methyl bromoacetate reaction, obtain the compound of formula 2
Wherein R represents CH
3or C
2h
5;
2) by the compound of described formula 2 under the alkaline condition that there is alkaline reagents, be hydrolyzed reaction, obtains compound 3
3) described compound 3 is carried out bromination reaction, obtain compound 4
4) described compound 4 and bromo-1, the 3-fluoro-2-iodobenzene of 5-are obtained by reacting compd A under the existence of transition metal, described transition metal is selected from the group be made up of copper and zinc.
2. the method for claim 1, wherein said step 3) in described bromination reaction be pass through
I) described compound 3 is refluxed in the solution with red precipitate and bromide reagent; Or
Ii) described compound 3 and plumbic acetate and bromide reagent refluxed in the solution carry out.
3. the method for claim 1, wherein said step 4) be
I) by described compound 4 and bromo-1, the 3-fluoro-2-iodobenzene of 5-in the solution, react under the existence of copper powder; Or
Ii) by described compound 4 and bromo-1, the 3-fluoro-2-iodobenzene of 5-in the solution, under the existence of zinc powder, and reaction is carried out under the existence of palladium catalyst and part.
4. the method for claim 1, wherein said step 1) temperature of reaction be 50 ~ 120 DEG C, the reaction times is 1 ~ 10h; Described step 2) temperature of reaction be 15 ~ 60 DEG C, the reaction times is 1 ~ 10h; Described step 3) temperature of reaction be 25 ~ 62 DEG C, the reaction times is 1 ~ 10h; And described step 4) temperature of reaction be 25 ~ 120 DEG C, the reaction times is 3 ~ 30h.
5. the method for claim 1, wherein said step 1), 2), 3) and 4) carry out all in the presence of an organic, described step 1), 2), 3) and 4) in described organic solvent be selected from independently of one another by C
1-C
4lower alcohol, methylene dichloride, methyl-sulphoxide, trifluoroacetic acid, ethyl acetate, DMF, tetrahydrofuran (THF), chloroform and combination composition group.
6. the method for claim 1, wherein said step 1) and 2) described in alkaline reagents be selected from the group be made up of sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, salt of wormwood, sodium carbonate, potassiumiodide, sodium bicarbonate, a hydronium(ion) Lithium Oxide 98min, diisopropyl ethylenediamine, triethylamine and combination thereof.
7. method as claimed in claim 2, wherein said step 3) described in bromide reagent be selected from the group be made up of bromine, N-bromosuccinimide, C5H6Br2N2O2, lithiumbromide, Sodium Bromide, Potassium Bromide and combination thereof.
8. method as claimed in claim 3, wherein said step 4) described in palladium catalyst be selected from by palladium, tetrakis triphenylphosphine palladium, Palladous chloride, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride, 1, two (diphenyl phosphine) ferrocene palladium chloride (II) chloride dichloromethane complex of 1'-, two (tricyclohexyl phosphine) palladium chloride, two (triphenylphosphine) palladium chloride (II), two (dibenzalacetone) palladium (0), three (dibenzalacetone) two palladium chloroform adducts, two (methyl ethyl diketone) palladium (II), palladium hydroxide charcoal, palladium carbon, (1, 5-cyclooctadiene) palladium chloride, two (acetonitrile) palladium chloride (II), the group of two (cyanophenyl) palladium chloride (II) and combination composition thereof.
9. method as claimed in claim 3, wherein said step 4) described in part be selected from by triphenylphosphine, tricyclohexyl phosphine, diphenylcyclohexyl phosphine, 4, the two diphenylphosphine-9 of 5-, 9-dimethyl xanthene, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 2-dicyclohexyl phosphine-2', 6'-dimethoxy-biphenyl, di-t-butyl cyclohexyl phosphine, three (o-tolyl) phosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 6'-diisopropoxy-1, 1'-biphenyl, Q-Phos, 1, two (diphenylphosphine) ferrocene of 1'-, 2-di-t-butyl phosphine-2 ', 4 ', the group of 6 '-tri isopropyl biphenyl and combination composition thereof.
10. method as claimed in claim 4, wherein said step 1) temperature of reaction be 60 ~ 100 DEG C, the reaction times is 2 ~ 6h; Described step 2) temperature of reaction be 20 ~ 40 DEG C, the reaction times is 1 ~ 5h; Described step 3) temperature of reaction be 40 ~ 62 DEG C, the reaction times is 1 ~ 5h; And described step 4) temperature of reaction be 25 ~ 80 DEG C, the reaction times is 5 ~ 24h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111154498A (en) * | 2020-01-19 | 2020-05-15 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
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| CN111154498A (en) * | 2020-01-19 | 2020-05-15 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
| CN111154498B (en) * | 2020-01-19 | 2021-10-22 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
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