CN112079862A - Carbonic acid ester liquid crystal intermediate and preparation method and application thereof - Google Patents
Carbonic acid ester liquid crystal intermediate and preparation method and application thereof Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004651 carbonic acid esters Chemical class 0.000 title description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000006239 protecting group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 26
- -1 4- (chlorocarbonyloxy) butyl Chemical group 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 6
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012351 deprotecting agent Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical group [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006545 (C1-C9) alkyl group Chemical group 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
Discloses a carbonic ester liquid crystal intermediate which is characterized in that the structural formula is shown as formula 1; wherein R1-R4 are each independently selected from the group consisting of a hydrogen atom, C1-10 alkyl or alkoxy, C1-10 alkyl or alkoxy- (C ═ O) -, halogen, CN; p represents a protecting group. The intermediate not only ensures that the product is easy to prepare and has higher yield, but also has higher purity; the product is further applied to the preparation of the carbonate liquid crystal material, and is beneficial to improving the purity of the carbonate liquid crystal material.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials; relates to a liquid crystal intermediate, a preparation method and application thereof; more particularly, relates to a carbonic ester liquid crystal intermediate, a preparation method and application thereof.
Background
In recent years, with the spread of broadcast and television display materials such as touch screens, liquid crystals have been particularly favored and developed for use as an essential part thereof, and with the research on liquid crystal materials, liquid crystal devices have been recently applied in the fields of beam deflectors, tunable prisms, field sequential displays, spatial light modulators, infrared scene generators, and the like, and in these optical applications, there is a case where a high demand is placed on the optical properties of liquid crystal materials.
Researches find that the high-symmetry carbonate liquid crystal material also has higher birefringence delta n and moderate rotational viscosity, and the FoM value of the response performance is usually larger, so that the high-symmetry carbonate liquid crystal material is suitable for being made into a liquid crystal optical device. However, at present, the yield of the product is low or even the product cannot be obtained stably due to instability of the intermediate.
In order to solve such problems, it is necessary that such products are relatively easy to prepare, have relatively high yield, are convenient to operate, use relatively low toxicity of reagents, and are more suitable for continuous industrial production.
The inventor surprisingly finds that the specific carbonate liquid crystal intermediate adopts a specific reaction route, so that the product is easier to prepare and has higher yield and higher purity; the product is further applied to the preparation of the carbonate liquid crystal material, and is beneficial to improving the purity of the carbonate liquid crystal material.
Disclosure of Invention
The invention aims to provide a carbonic ester liquid crystal intermediate, a preparation method and application thereof.
In order to achieve the above objects, in one aspect, the present invention provides a liquid crystal carbonate intermediate, which has a structural formula represented by formula 1:
wherein R1-R4 are each independently selected from hydrogen atom, C1-10Alkyl or alkoxy, C1-10Alkyl or alkoxy- (C ═ O) -, halogen, CN; p represents a protecting group.
Specifically, C1-10Alkyl or alkoxy packetsDraw C1-9Alkyl or alkoxy, C1-8Alkyl or alkoxy, C1-7Alkyl or alkoxy, C1-6Alkyl or alkoxy, C1-5Alkyl or alkoxy, C1-4Alkyl or alkoxy, C1-3Alkyl or alkoxy, C1-2Alkyl or alkoxy.
More specifically, C1-10Alkyl or alkoxy includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, 4-heptyl, octyl, 2-octyl, 3-octyl, 4-octyl, nonyl, 2-nonyl, 3-nonyl, 4-nonyl, 5-nonyl, decyl, 2-decyl, 3-decyl, 4-decyl, 5-decyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, heptyloxy, pentyl-oxy, 2-heptyloxy, 3-heptyloxy, 4-heptyloxy, octyloxy, 2-octyloxy, 3-octyloxy, 4-octyloxy, nonyloxy, 2-nonyloxy, 3-nonyloxy, 4-nonyloxy, 5-nonyloxy, decyloxy, 2-decyloxy, 3-decyloxy, 4-decyloxy, 5-decyloxy.
In a specific embodiment, C1-10Alkyl or alkoxy groups include methyl, ethyl, methoxy, ethoxy.
The aforementioned liquid crystal intermediate according to the present invention, wherein R1 and R4 are each independently selected from a hydrogen atom or C1-10Alkyl or alkoxy- (C ═ O) -; r2 and R3 are selected from hydrogen atoms.
In a specific embodiment, R1 and R4 are selected from C1-10Alkyl or alkoxy- (C ═ O) -; r2 and R3 are selected from hydrogen atoms.
In another specific embodiment, R1, R2, and R3 are selected from hydrogen atoms; r4 is selected from C1-10Alkyl or alkoxy- (C ═ O) -.
The liquid crystal intermediate according to the present invention, wherein R1, R2 and R3 are selected from hydrogen atoms; r4 is selected from C1-10Alkoxy- (C ═ O) -.
In a particular embodiment, R1, R2 and R3 are selected from hydrogen atoms; r4 is selected from C1Alkoxy- (C ═ O) -.
On the other hand, the invention provides a liquid crystal compound, which is characterized in that the structural formula is shown as formula 2:
wherein R1-R4 are as previously defined.
In a particular embodiment, R1, R2 and R3 are selected from hydrogen atoms; r4 is selected from C1Alkoxy- (C ═ O) -. That is, the liquid crystal compound is selected from compounds of formula 2-1:
in another aspect, the present invention provides a method for preparing the liquid crystal intermediate according to the present invention, wherein 2-hydroxy-6-naphthoic acid is used as a raw material, and is protected and condensed with the compound of formula 3,
to obtain the compound of formula 1.
According to the preparation method, tert-butyldimethylsilyl chloride (TBSCl) is used as a protecting group in the protection step, and the protection product is obtained by reaction under the action of an acid binding agent.
Advantageously, 2-hydroxy-6-naphthoic acid: TBSCl: the equivalent ratio of the acid binding agent is 1: 1-1.2: 1.2 to 5.
In a particular embodiment, the acid scavenger is selected from triethylamine.
Advantageously, the reaction time is between 6 and 12 hours.
According to the preparation method, Dicyclohexylcarbodiimide (DCC) is used as a condensing agent and 4-Dimethylaminopyridine (DMAP) is used as a catalyst in the condensation step, and the compound shown in the formula 3 reacts with the protection product to obtain the compound shown in the formula 1.
Advantageously, the compound of formula 3: equivalent ratio of protected product 1: 2 to 2.5.
DCC and DMAP are advantageously used in amounts of 5-20% and 200-250% respectively of the equivalent of the compound of formula 3.
In still another aspect, the present invention provides a method for preparing a liquid crystal compound, wherein the compound of formula 2 is obtained by deprotecting a liquid crystal intermediate according to the present invention under the action of a deprotecting agent.
The preparation method of the invention, wherein the deprotection agent is selected from tetrabutylammonium fluoride (TBAF).
Advantageously, the compounds of formula 1: equivalent ratio of deprotecting agent 1: 2.1 to 2.5.
In a final aspect, the invention provides an application of the liquid crystal compound to prepare a highly-symmetric carbonate liquid crystal material, which is characterized in that the compound of formula 2 reacts with 4- (chlorocarbonyloxy) butyl acrylate (VE4Cl) under the action of an acid-binding agent to obtain the highly-symmetric carbonate liquid crystal material.
Advantageously, the compound of formula 2: VE4 Cl: the equivalent ratio of the acid binding agent is 1: 2.1-2.5: 2.5 to 3.
In a particular embodiment, the acid scavenger is selected from triethylamine.
Without wishing to be bound by any theory, when starting from a specific carbonate liquid crystal intermediate, a specific reaction route is adopted, so that the product is easy to prepare, has higher yield and higher purity; the product is further applied to the preparation of the carbonate liquid crystal material, and is beneficial to improving the purity of the carbonate liquid crystal material.
Drawings
FIG. 1 is an HPLC chromatogram of the final product of example 2 of the present invention;
FIG. 2 is a HNMR map of the final product of example 2 of the present invention;
FIG. 3 is an HPLC chromatogram of a final product of an application example of the present invention;
FIG. 4 is a HNMR map of the final product of an application example of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the invention. Unless otherwise indicated, percentages in the examples are uniformly percentages by mass.
Example 1
Protection: 20g of 2-hydroxy-6-naphthoic acid and 100mL of DCM are put into a 250mL three-neck flask with magnetons, 12.9g of triethylamine is added, the temperature is reduced to 0 ℃, 17.6g of TBSCl is started to stir for 0.5h finally, the temperature is kept for 0.5h at room temperature, and after TLC analysis detects that no 2-hydroxy-6-naphthoic acid is considered to reach the end point of the reaction, the post-treatment is carried out.
After-treatment, the reaction solution is washed by water and then liquid is separated, after the organic phase is dried, DCM is removed by rotary evaporation, and the final white solid is 30.65 g; the yield thereof was found to be 95.36%.
Condensation: 30g of protection product, 7.58g of 2, 5-dihydroxy methyl benzoate and 150mL of DCM are put into a 250mL three-neck flask with magnetons, 0.5g of DMAP0 is added, DCC-DCM (20g of DCC is dissolved in 40mL) solution is slowly dripped after the temperature is reduced to 5 ℃, the temperature is controlled not to exceed 15 ℃ in the dripping process, the DCC-DCM solution is naturally heated to room temperature after the dripping is finished and is kept overnight at the room temperature, and no raw material is considered to reach the reaction endpoint after TLC analysis and detection.
And (3) post-treatment, namely adding 50mL of water into the reaction solution, stirring for 1h to quench DCC, filtering, separating the filtrate from an organic phase, drying and spin-drying to obtain 23.26g of white solid with the yield of 70%.
Example 2
Deprotection: THF110mL, example 1 white solid 22g, TBAF 17.95g, was placed in a 250mL three-necked flask equipped with magnetons, and the mixture was allowed to stand at room temperature overnight. After TLC monitoring, no raw material remained, the post-treatment was carried out.
And (3) post-treatment: after the solvent was spin-dried, the crude product was slurried with a small amount of DCM and filtered to give 10.12g of a white solid; the yield thereof was found to be 66.67%.
FIG. 1 is an HPLC chromatogram of the final product of example 2 of the present invention; figure 2 is a final product HNMR map of example 2 of the present invention.
Application examples
10g of the final product in example 2, 5.97g of triethylamine and 100mL of DCM are put into a 250mL three-neck flask with magnetons, stirring is started, VE4Cl-DCMaq (10.16gVE4Cl is dissolved in 10mL) is dripped into an ice-water bath when T is less than or equal to 5 ℃, the process control temperature is not more than 10 ℃, stirring is carried out at room temperature for 4h after dripping is finished, and the reaction can be stopped for post-treatment by monitoring that the residual content of raw materials is less than 0.3 percent through HPLC;
and (3) post-treatment, namely adding 5% HCL10ml into the reaction solution, washing twice, removing triethylamine, separating liquid, drying an organic phase, passing through a silica gel column filled with 1 time of product mass of silica gel, and spin-drying the solvent. The resulting solid was slurried with 200mL of methanol for 1h and then filtered to give 15.62g of the final product in 93.59% yield.
FIG. 3 is an HPLC chromatogram of a final product of an application example of the present invention; FIG. 4 is a HNMR map of the final product of an application example of the present invention.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. A carbonate liquid crystal intermediate is characterized in that the structural formula is shown as formula 1:
wherein R1-R4 are each independently selected from hydrogen atom, C1-10Alkyl or alkoxy, C1-10Alkyl or alkoxy- (C ═ O) -, halogen, CN; p represents a protecting group.
2. A liquid crystal intermediate according to claim 1, wherein R1 and R4 are each independently selected from a hydrogen atom or C1-10Alkyl or alkoxy- (C ═ O) -; r2 and R3 are selected from hydrogen atoms.
3. A liquid crystal intermediate according to claim 2, wherein R1, R2 and R3 are selected from hydrogen atoms; r4 is selected from C1-10Alkoxy- (C ═ O) -.
4. A liquid crystal compound, characterized in that its structural formula is shown in formula 2:
wherein R1-R4 are as previously defined.
5. The liquid crystal compound of claim 4, further selected from compounds of formula 2-1:
6. a method for preparing a liquid crystal intermediate according to claim 1, wherein 2-hydroxy-6-naphthoic acid is used as a raw material, protected and condensed with a compound of formula 3,
to obtain the compound of formula 1.
7. The preparation method of claim 6, wherein the protection step is implemented by providing a protection group with tert-butyldimethylsilyl chloride (TBSCl) and reacting under the action of an acid-binding agent to obtain a protection product.
8. The method of claim 6, wherein the condensing step comprises reacting the compound of formula 3 with the protected product to obtain the compound of formula 1 using Dicyclohexylcarbodiimide (DCC) as a condensing agent and 4-Dimethylaminopyridine (DMAP) as a catalyst.
9. A method for producing a liquid crystal compound according to claim 4, wherein the compound of formula 2 is obtained by deprotecting the liquid crystal intermediate according to claim 1 with a deprotecting agent.
10. The application of the liquid crystal compound in preparing the highly-symmetric carbonate liquid crystal material according to claim 4, wherein the compound shown in the formula 2 is reacted with 4- (chlorocarbonyloxy) butyl acrylate (VE4Cl) under the action of an acid-binding agent to obtain the highly-symmetric carbonate liquid crystal material.
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| CN1179153A (en) * | 1995-03-24 | 1998-04-15 | 巴斯福股份公司 | Liquid crystal compounds |
| CN101052613A (en) * | 2004-11-04 | 2007-10-10 | 株式会社艾迪科 | Polymerizable compound and composition containing the polymerizable compound |
| CN101175836A (en) * | 2005-05-11 | 2008-05-07 | 巴斯福股份公司 | Compounds comprising 2,6-naphthyl groups |
| CN109803950A (en) * | 2016-07-21 | 2019-05-24 | 三菱瓦斯化学株式会社 | Compound, resin and composition and corrosion-resisting pattern forming method and circuit pattern forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179153A (en) * | 1995-03-24 | 1998-04-15 | 巴斯福股份公司 | Liquid crystal compounds |
| CN101052613A (en) * | 2004-11-04 | 2007-10-10 | 株式会社艾迪科 | Polymerizable compound and composition containing the polymerizable compound |
| CN101175836A (en) * | 2005-05-11 | 2008-05-07 | 巴斯福股份公司 | Compounds comprising 2,6-naphthyl groups |
| CN109803950A (en) * | 2016-07-21 | 2019-05-24 | 三菱瓦斯化学株式会社 | Compound, resin and composition and corrosion-resisting pattern forming method and circuit pattern forming method |
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