CN105481662B - The method for preparing the intermediate for producing the liquid-crystal compounds containing difluoro-methoxy - Google Patents
The method for preparing the intermediate for producing the liquid-crystal compounds containing difluoro-methoxy Download PDFInfo
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- 0 *c(cc1F)cc(F)c1F Chemical compound *c(cc1F)cc(F)c1F 0.000 description 3
- NBEVZZHOXVDGHV-UHFFFAOYSA-N CCCC(C1)Cc2c1ccc(-c1ccc(-c3cc(N)c(C(N)(N)Oc(cc4N)cc(C(C)=C)c4N)c(N)c3)c(N)c1)c2 Chemical compound CCCC(C1)Cc2c1ccc(-c1ccc(-c3cc(N)c(C(N)(N)Oc(cc4N)cc(C(C)=C)c4N)c(N)c3)c(N)c1)c2 NBEVZZHOXVDGHV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of method for preparing the midbody compound A for producing the liquid-crystal compounds containing difluoro-methoxy.The compound A is made by initial feed of 3,4,5 trifluoromethyl phenols.Methods described is easy to operate, cost is low, high income, is adapted to industrialized production.
Description
Technical field
The present invention relates to field of liquid crystals, and in particular to a kind of to prepare for producing in liquid-crystal compounds containing difluoro-methoxy
The application of the method for mesosome and the midbody compound in liquid-crystal compounds is prepared.
Background technology
Since 1988 find liquid crystal, due to liquid crystal has many unique properties and before having a wide range of applications
Scape.For example, in chemical industry, liquid crystal can promote organic chemistry orientation reaction as orderly solvent, and alloisomerism is selected,
Optical rotatory substance is enriched with and separated, and chromatogram selectivity and separative efficiency can be improved as Stationary liquids；Liquid crystal state functional membrane
With selective penetrating quality most good separative efficiency.In the electronics industry, liquid crystal is not due to can with many other materials
The superior property of analogy, such as：Power consumption is extremely low, and driving voltage is low, fast response time, display etc. under bright light environments, so that in electricity
Increasingly it is widely applied in terms of sub-display technology and microelectronics.Just because of above-mentioned successful application and development, promote
People are made to synthesize the liquid-crystal compounds different with studying up to ten thousand kinds.
In the late two decades, liquid crystal material is widely used in industry and the daily life of people due to its unique photoelectric properties
In work.As a kind of new display material, it not only has, and power consumption is extremely low, driving voltage is low, fast response time, in bright ring
The particular advantages shown under border, also with size flexibly, panelized, meandering, show clear, applied widely, cost it is low
Feature.Therefore, as people are to liquid crystal display quality requirements more and more higher, in order to meet wanting for liquid crystal display device development
Ask, the requirement for reducing the viscosity and increase dielectric anisotropy of mixed liquid crystal is extremely urgent, therefore it is required that exploitation is highly polar, low viscous
The monomer liquid crystal and its synthetic method of degree.
At present, the monomer liquid crystal with high dielectric anisotropy and low viscosity is mainly the monomer liquid containing difluoro-methoxy
Crystallization compound, is widely used in TFT-LCD mixed liquid crystals with the liquid-crystal compounds.LCD compound with difluoro-methoxy
Thing, because Stability Analysis of Structures causes its electric charge conservation rate high；Dipole moment is increased, and is caused its dielectric anisotropy larger, is conducive to satisfying
With the reduction of 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.
Difluoro-methoxy is introduced in liquid crystal molecule skeleton a variety of methods, there is a variety of tell about in different documents.
CN1628165A discloses compound A
A kind of preparation method, this method is with 3,5, and-difluoro bromobenzene is raw material, by a series of preparing of reaction
Compound A.The process employs expensive and big toxicity sulphur reagent, low yield and reaction complexity are not suitable for extensive raw
Production.
As the key intermediate for preparing the liquid-crystal compounds containing difluoro-methoxy, compound A is used to prepare LCD compound
Thing is disclosed in CN1628165A and CN102477305A.
In order to solve problems of the prior art, the invention provides a kind of new side for prepare compound A
Method, the compound A can be used to prepare the monomer liquid crystal compound containing difluoro-methoxy as intermediate.Methods described with
Cheap and easily-available 3,4,5- trifluoromethyl phenols are raw material, and the intermediate for often walking reaction is all easy to purification, and yield is higher, is adapted to work
Industry metaplasia is produced.
The content of the invention
It is an object of the invention to provide a kind of for prepare compound A's for above shortcomings in the prior art
It is easy to the new preparation method of purification, higher yield, reduction actual production operation difficulty and cost.The compound A can conduct
Intermediate, to prepare the liquid-crystal compounds containing difluoro-methoxy.
One aspect of the invention provides compound A preparation method, successively including following 4 steps：
Specifically, the present invention provides a kind of prepare compound A method, the described method comprises the following steps：
1) by compound 1
Under the alkalescence condition that there is alkaline reagent, and ethyl bromide difluoride or the reaction of difluoro methyl bromoacetate, obtain
The compound of formula 2
Wherein R represents CH3Or C2H5；
2) by the compound of the formula 2 under the alkalescence condition that there is alkaline reagent, reaction is hydrolyzed, compound is obtained
3
3) compound 3 is subjected to bromination reaction, obtains compound 4
4) by the compound 4 and the fluoro- 2- iodobenzenes of the bromo- 13- of 5-
Reaction obtains compound A in the presence of transition metal, and the transition metal is selected from the group being made up of copper and zinc.
In preparation method of the present invention, the step 3) in compound 4 preparation method for following method i) or
Method ii) in any one：
I) by the compound 3 and mercury oxide red and bromide reagent back flow reaction in a solvent, pass through after completion of the reaction
Later handle, obtain compound 4；Or
Ii) by the compound 3 and lead acetate and bromide reagent back flow reaction in a solvent, after passing through after completion of the reaction
Processing, obtains the compound 4.
In preparation method of the present invention, the step 4) in compound A preparation methods be following method i)：
I) by the compound 4,5- bromo- 1, the fluoro- 2- iodobenzenes of 3- and copper powder are added in solvent and reacted, after completion of the reaction
By post processing, the compound A is obtained.
In preparation method of the present invention, the step 4) in compound A preparation methods be following method ii)：
Ii) compound 4 and zinc powder are added in solvent and reacted, palladium catalyst, part and 5- is then added bromo-
1,3- fluoro- 2- iodobenzenes, continue to react, after completion of the reaction by post processing, obtain the compound A.
In preparation method of the present invention, the step 1) reaction temperature be 50~120 DEG C, the reaction time is 1
~10h, preferable reaction temperature is 60~100 DEG C, and the reaction time is 2~6h.
In preparation method of the present invention, the step 2) reaction temperature be 15~60 DEG C, the reaction time is 1~
10h, preferable reaction temperature is 20~40 DEG C, and the reaction time is 1~5h.
In preparation method of the present invention, the step 3) reaction temperature be 25~62 DEG C, the reaction time is 1~
10h, preferable reaction temperature is 40~62 DEG C, and the reaction time is 1~5h.
In preparation method of the present invention, the step 4) reaction temperature be 25~120 DEG C, the reaction time is 3
~30h, preferable reaction temperature is 25~80 DEG C, and the reaction time is 5~24h.
In preparation method of the present invention, the step 1), 2), 3) He 4) be to carry out in the presence of an organic
, the step 1), 2), 3) He 4) in the organic solvent be each independently selected from by C1-C4Lower alcohol, dichloromethane,
The group of dimethyl sulfoxide, trifluoroacetic acid, ethyl acetate, N,N-dimethylformamide, tetrahydrofuran, chloroform and combinations thereof composition.
In preparation method of the present invention, the step 1) and 2) described in alkaline reagent be selected from by sodium hydride, hydrogen
Sodium oxide molybdena, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, KI, sodium acid carbonate, a hydronium(ion) lithia, diisopropyl
The group of base ethylenediamine, triethylamine and combinations thereof composition.
In preparation method of the present invention, the step 3) described in bromide reagent be selected from by bromine, N- bromo ambers
The group of amber acid imide, C5H6Br2N2O2, lithium bromide, sodium bromide, KBr and combinations thereof composition.
In preparation method of the present invention, the step 4) described in palladium catalyst be selected from by palladium, four (triphens
Base phosphine) palladium, palladium bichloride, [1,1'- double (diphenylphosphine) ferrocene] palladium chloride, double (diphenyl phosphine) the ferrocene dichloros of 1,1'-
Change palladium (II) chloride dichloromethane complex, double (tricyclohexyl phosphine) palladium chlorides, double (triphenylphosphine) palladium chlorides (II), two (two
BENZYLIDENE ACETONE) palladium (0), three (dibenzalacetone) two palladium chloroform adducts, two (acetylacetone,2,4-pentanedione) palladiums (II), palladium dydroxide
Charcoal, palladium carbon, (1,5- cyclo-octadiene) palladium chloride, two (acetonitrile) palladium chlorides (II), two (cyanophenyl) palladium chlorides (II) and its
Combine the group of composition.
In some embodiments it is preferred that the palladium catalyst be selected from by tetrakis triphenylphosphine palladium, palladium bichloride, palladium,
The group of double (dibenzyl subunit acetone) palladiums and combinations thereof composition.
In preparation method of the present invention, the step 4) in part be selected from by triphenylphosphine, tricyclohexyl phosphine,
Double diphenylphosphine -9,9- dimethyl the xanthenes of diphenylcyclohexyl phosphine, 4,5-, 2- dicyclohexylphosphontetrafluoroborates -2', 4', 6'- triisopropyl
Biphenyl, 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, di-t-butyl cyclohexyl phosphine, three (o-tolyl) phosphines, the hexamethylenes of 2- bis-
Base phosphine -2', 6'- diisopropoxy -1,1'- biphenyl, double (diphenylphosphine) ferrocene of Q-Phos, 1,1'-, 2- di-t-butyls phosphine -
The group of 2', 4', 6'- tri isopropyl biphenyl and combinations thereof composition.
In some embodiments it is preferred that the part is selected from by 2- dicyclohexylphosphontetrafluoroborates -2', 6'- diisopropoxy -1,
1'- biphenyl, double (diphenylphosphine) ferrocene of Q-Phos, 1,1'-, 2- di-t-butyl phosphines -2', 4', 6'- tri isopropyl biphenyl and its
Combine the group of composition.
Compound A of the present invention can prepare liquid-crystal compounds containing difluoro-methoxy as intermediate.
The advantage of the invention is that：This method has the advantage that：
1. needed for supplementary material be commercially available industrial chemicals, buying cost is low, so as to reduce production cost；
2. purity is high, yield is good；
3. reaction condition is gentle, and it is simple to operate, be suitable for industrialized production；
4. overcoming taste present in prior art and the big defect of toxicity, danger is reduced.
Therefore, implementation cost can be substantially reduced using the preparation method of the present invention, is advantageously implemented industrialized production, has
High industrial application value.
It will be understood by those skilled in the art that above-mentioned reaction condition, includes foregoing synthesis compound A reaction condition,
It is not the sole mode for realizing technical solution of the present invention.Those skilled in the art can be on the basis for not departing from present inventive concept
On, the reaction condition is modified and realizes technical scheme according to being actually needed.
Brief description of the drawings
Fig. 1 is the MS figures of compound 2；
Fig. 2 is compound 31H-NMR schemes；
Fig. 3 is the MS figures of compound 4；
Fig. 4 is compound A MS figures；
Fig. 5 is the MS figures of compound 6；And
Fig. 6 is the MS figures of compound 8.
Embodiment
Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention
Example, only for illustrating the present invention, and be not limited to the present invention.
In following examples, in addition to compound A, compound 2, compound 3 and compound 4, remaining used chemical combination
Thing monomer and related reagent are commercially available.Wherein,Reagent name be 3,4,5- trifluoromethyl phenols, CAS
Number be 99627-05-1,Reagent name be the fluoro- 2- iodobenzenes of bromo- 1, the 3- of 5-, No. CAS be 160976-02-3.
Embodiment 1
1) preparation of compound 2
Weigh 14.8g compounds 1 to be added in 80mL tetrahydrofurans, sodium hydride (60%, 4.4g) be added portionwise at room temperature,
1h is stirred after adding, it is disposable to add 21g ethyl bromide difluorides, 80 DEG C are warming up to, 3h is reacted.Plus 100mL water, 200mL*3
Ethyl acetate aqueous phase extracted, dries, is spin-dried for.Plus the silica gel mixed sample of the mesh of 40g 100~200,200~300 mesh silica gel of 3 times of pad,
50：1 petroleum ether and the mixed solvent 1L of ethyl acetate rinse post, obtain 25g yellow solids (compound 2).GC：99.2%,
Yield：92%.
The MS figures of compound 2 are referring to Fig. 1.
2) preparation of compound 3
25g compounds 2 and the hydronium(ion) lithias of 8g mono- are weighed, the in the mixed solvent of 80mL methanol and 50mL water is dissolved in,
25 DEG C of reaction 3h, are extracted with 300mL ethyl acetate, dry, be spin-dried for, obtain 22g white solids (compound 3), yield：98%.
1H-NMR(d6-DMSO)δ：8.466(d,1H)；8.132(s,1H).
Compound 31H-NMR figures are referring to Fig. 2.
3) preparation of compound 4
Weigh 22g compounds 3 to be dissolved in 100mL chloroforms, 23g mercury oxide reds are added at 40 DEG C, are then slowly added dropwise
32g bromines, back flow reaction 4h is cooled down, filtering, adds 100mL water, and the extraction of 200mL*3 ethyl acetate is dried, is spin-dried for, obtains
10g compounds 4.GC：99.2%, yield：41%.
The MS figures of compound 4 are referring to Fig. 3.
4) compound A preparation
18g compounds 4 are weighed, the fluoro- 2- iodobenzenes of bromo- 1, the 3- of 21g 5-, 25g copper powders are added in 250mL dimethyl sulfoxides, 80 DEG C
24h is reacted, addition 300mL water has been reacted, 3*300mL ethyl acetate extraction, 100mL*3 washing ethyl acetate is dried, is spin-dried for,
Obtain 22g compounds A.GC：99.2%, yield：88%.
Compound A MS figures are referring to Fig. 4.
Embodiment 2
1) preparation of compound 4
The compound 3 for weighing the synthesis of 22g embodiments 1 is dissolved in 100mL chloroforms, 25g lead acetates is added at 40 DEG C, then
20g lithium bromides are added portionwise, back flow reaction 4h is cooled down, filtering, add 100mL water, the extraction of 200mL*3 ethyl acetate is dried,
It is spin-dried for, obtains 9g compounds 4.GC：99.2%, yield：38%.
2) compound A preparation
Weigh 18g compounds 4,8.5g zinc powders to be added in 150mL DMFs, 25 DEG C of reaction half an hour.So
0.5g palladiums, 1g 1, double (diphenylphosphine) ferrocene of 1'- and the fluoro- 2- iodobenzenes of bromo- 1, the 3- of 21g 5-, 40 DEG C of reactions are added afterwards
5h, has reacted addition 300mL water, and 3*300mL ethyl acetate extraction, 100mL*3 washing ethyl acetate is dried, is spin-dried for, obtains
22g compounds A.GC：99.2%, yield：88%.
Embodiment 3
Weigh 18g compounds 5,21g compounds A, 16g potassium carbonate, 0.7g 4- (3- Phenylphosphines palladium) be added to 150mL toluene,
The in the mixed solvent of 50mL ethanol and 50mL water, back flow reaction 2h has reacted addition 100mL water, 3*300mL ethyl acetate extraction
Take, 100mL*3 washing ethyl acetate, dry, be spin-dried for, plus the mesh of 40g 200~300 silica gel, it is thick cross post, be spin-dried for, obtain 25gization
Compound 6 (known liquid-crystal compounds, referring to CN102477305A), GC：99.2%, yield：92%.
The MS figures of compound 6 are referring to Fig. 5.
Embodiment 4
Weigh 18g compounds 7,21g compounds A, 16g potassium carbonate, 0.7g 4- (3- Phenylphosphines palladium) be added to 150mL toluene,
The in the mixed solvent of 50mL ethanol and 50mL water, back flow reaction 2h has reacted addition 100mL water, 3*300mL ethyl acetate extraction
Take, 100mL*3 washing ethyl acetate, dry, be spin-dried for, plus the mesh of 40g 200~300 silica gel, it is thick cross post, be spin-dried for, obtain 25gization
Compound 8 (known liquid-crystal compounds, referring to CN102477305A), GC：99.3%, yield：92%.
The MS figures of compound 8 are referring to Fig. 6.
Claims (7)
1. a kind of prepare compound A method
It the described method comprises the following steps：
1) by compound 1
Under the alkalescence condition that there is alkaline reagent, and ethyl bromide difluoride or the reaction of difluoro methyl bromoacetate, obtain formula 2
Compound
Wherein R represents CH3Or C2H5；
2) by the compound of the formula 2 under the alkalescence condition that there is alkaline reagent, reaction is hydrolyzed, compound 3 is obtained
3) compound 3 and mercury oxide red and bromide reagent are flowed back carry out bromination reaction in the solution；Or by institute
State compound 3 and flow back into row progress bromination reaction in the solution with lead acetate and bromide reagent, obtain compound 4
4) by the compound 4 and 5- bromo- 1, the fluoro- 2- iodobenzenes of 3- in the solution, react in the presence of copper powder；Or will be described
Compound 4 and the fluoro- 2- iodobenzenes of bromo- 1, the 3- of 5- in the solution, in the presence of zinc powder, and in the presence of palladium catalyst and part
Lower reaction is carried out；
Wherein described step 3) described in bromide reagent be selected from by bromine, N-bromosuccinimide, C5H6Br2N2O2, lithium bromide,
The group of sodium bromide, KBr and combinations thereof composition.
2. the method as described in claim 1, wherein the step 1) reaction temperature be 50~120 DEG C, the reaction time is 1~
10h；The step 2) reaction temperature be 15~60 DEG C, the reaction time be 1~10h；The step 3) reaction temperature be 25
~62 DEG C, the reaction time is 1~10h；And the step 4) reaction temperature be 25~120 DEG C, the reaction time be 3~30h.
3. the method as described in claim 1, wherein the step 1), 2), 3) He 4) be to carry out in the presence of an organic
, the step 1), 2), 3) He 4) in the organic solvent be each independently selected from by C1-C4Lower alcohol, dichloromethane,
The group of dimethyl sulfoxide, trifluoroacetic acid, ethyl acetate, N,N-dimethylformamide, tetrahydrofuran, chloroform and combinations thereof composition.
4. the method as described in claim 1, wherein the step 1) and 2) described in alkaline reagent be selected from by sodium hydride, hydrogen-oxygen
Change sodium, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, KI, sodium acid carbonate, a hydronium(ion) lithia, diisopropyl
The group of ethylenediamine, triethylamine and combinations thereof composition.
5. the method as described in claim 1, wherein the step 4) described in palladium catalyst be selected from by palladium, four (triphens
Base phosphine) palladium, palladium bichloride, [1,1'- double (diphenylphosphine) ferrocene] palladium chloride, double (diphenyl phosphine) the ferrocene dichloros of 1,1'-
Change palladium (II) chloride dichloromethane complex, double (tricyclohexyl phosphine) palladium chlorides, double (triphenylphosphine) palladium chlorides (II), two (two
BENZYLIDENE ACETONE) palladium (0), three (dibenzalacetone) two palladium chloroform adducts, two (acetylacetone,2,4-pentanedione) palladiums (II), palladium dydroxide
Charcoal, palladium carbon, (1,5- cyclo-octadiene) palladium chloride, two (acetonitrile) palladium chlorides (II), two (cyanophenyl) palladium chlorides (II) and its
Combine the group of composition.
6. the method as described in claim 1, wherein the step 4) described in part be selected from by triphenylphosphine, thricyclohexyl
Double diphenylphosphine -9,9- dimethyl the xanthenes of phosphine, diphenylcyclohexyl phosphine, 4,5-, 2- dicyclohexylphosphontetrafluoroborates -2', 4', 6'- tri- are different
Pentylbiphenyl, 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, di-t-butyl cyclohexyl phosphine, three (o-tolyl) phosphines, 2- bis-
Cyclohexyl phosphine -2', 6'- diisopropoxy -1,1'- biphenyl, the phenyl -1'- of 1,2,3,4,5- penta (di-t-butyl phosphorus base) ferrocene,
1,1'- double (diphenylphosphine) ferrocene, 2- di-t-butyls phosphines -2 ', the group of 4 ', 6 '-tri isopropyl biphenyl and combinations thereof composition.
7. method as claimed in claim 2, wherein the step 1) reaction temperature be 60~100 DEG C, the reaction time is 2~
6h；The step 2) reaction temperature be 20~40 DEG C, the reaction time be 1~5h；The step 3) reaction temperature for 40~
62 DEG C, the reaction time is 1~5h；And the step 4) reaction temperature be 25~80 DEG C, the reaction time be 5~24h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002004119A1 (en) * | 2000-07-11 | 2002-01-17 | Bp Chemicals Limited | Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group |
| CN1628165A (en) * | 2001-10-17 | 2005-06-15 | 默克专利股份有限公司 | Liquid crystal compounds |
| CN101294079A (en) * | 2002-11-27 | 2008-10-29 | 默克专利股份有限公司 | Liquid crystalline compounds |
| EP2239056A1 (en) * | 2009-04-09 | 2010-10-13 | Saudi Basic Industries Corporation | Catalyst composition and process for oligomerization of ethylene |
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2014
- 2014-09-18 CN CN201410480048.7A patent/CN105481662B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002004119A1 (en) * | 2000-07-11 | 2002-01-17 | Bp Chemicals Limited | Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group |
| CN1628165A (en) * | 2001-10-17 | 2005-06-15 | 默克专利股份有限公司 | Liquid crystal compounds |
| CN101294079A (en) * | 2002-11-27 | 2008-10-29 | 默克专利股份有限公司 | Liquid crystalline compounds |
| EP2239056A1 (en) * | 2009-04-09 | 2010-10-13 | Saudi Basic Industries Corporation | Catalyst composition and process for oligomerization of ethylene |
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