Search

CN-122010978-A - Synthesis of chiral photochromic dye containing endogenous and exogenous and liquid crystal application thereof

CN122010978ACN 122010978 ACN122010978 ACN 122010978ACN-122010978-A

Abstract

The invention provides synthesis of a chiral photochromic dye containing endogenous and exogenous and liquid crystal application thereof. The steric type diaryl ethylene is used as a matrix, the endogenous chirality and the exogenous chirality are integrated into a single molecule for the first time, and the internal and external source chiral dynamic optical switch based on the steric type diaryl ethylene is provided. The method is obtained by determining whether binaphthol is bridged or not, changing the bridging length of binaphthol and introducing side chain alkyl to change the molecular structure. The RBNBT series of molecules synthesized by the invention have the characteristics of high thermal stability and strong fatigue resistance, and two different diastereoisomers, (R, M, R) -RBNBT series of molecules and (R, P, R) -RBNBT series of molecules can be formed through chiral resolution.

Inventors

  • ZHU WEIHONG
  • WANG XIANGLI
  • GAN JIAAN
  • LI MENGQI
  • HU HONGLONG
  • ZHANG TONGYUN
  • YIN FANGYUAN

Assignees

  • 华东理工大学
  • 上海甘田光学材料有限公司

Dates

Publication Date
20260512
Application Date
20251230

Claims (10)

  1. 1. A dynamic optical switch molecule containing endogenous chirality and exogenous chirality is characterized in that steric hindrance diaryl ethylene is used as a matrix, and the structural general formula is shown in the following formula I: , (I) in formula I, n=0, 1,2, 3 or 4, R 1 , R 2 , R 3 , R 4 is selected from Any one of them.
  2. 2. The dynamic optical switch molecule of claim 1, wherein the specific structure is selected from any one of the following: , 。
  3. 3. A method for preparing a dynamic optical switch molecule containing an endogenous chirality and an exogenous chirality as claimed in claim 1 or 2, comprising the steps of: (1) Adding R-binaphthol and a1, 4-dibutyl halogen substituent into a reaction container which is dried at a high temperature, wherein the molar ratio of the R-binaphthol to the 1, 4-dibutyl halogen substituent is 1:2-6, then adding carbonate and an aprotic polar organic solvent, and separating by silica gel column chromatography to obtain a pale yellow solid after complete reflux reaction at 80 ℃ under the protection of inert gas; (2) Adding the product obtained in the step (1) and the anhydrous aprotic polar organic solvent into a reaction vessel which is dried at a high temperature, cooling to-79 ℃, slowly adding n-butyllithium, fully stirring for a certain time, adding 1, 2-dihalogen substituted tetrachloroethane dissolved by the same aprotic polar organic solvent, wherein the amount of the substances is 1-4 times that of the product obtained in the step 1, completely reacting at a low temperature, shifting to room temperature, adding a small amount of water quenched butyllithium after the point plate monitoring reaction is complete, and separating by silica gel column chromatography to obtain white solid; (3) Adding the product obtained in the step (2) and tetrahydroxy diboron into a three-mouth bottle which is dried at high temperature according to the mol ratio of 1:3.5, then sequentially adding potassium acetate, X-Phos, xphos Pd G, methanol, refluxing and concentrating the reaction liquid at 80 ℃ under the protection of nitrogen, and separating by silica gel column chromatography to obtain white solid; (4) And (3) dissolving the product of the step (3) and BBTE-2 halogen substituent in an aprotic polar organic solvent according to a molar ratio of 2-4.5:1 in a single-port bottle, adding an aqueous solution of carbonate, adding 5wt% of triphenylphosphine palladium in a nitrogen atmosphere, carrying out reflux reaction at 75 ℃, concentrating the reaction solution after the TLC monitoring reaction is finished, and separating by silica gel column chromatography to obtain a red powder end product.
  4. 4. The method for preparing the dynamic optical switch molecule containing the endogenous chirality and the exogenous chirality according to claim 3, wherein: In step (1), the high temperature dried reaction vessel is selected from flame dried vessels; The 1, 4-di-butane halogen substituent is selected from 1, 4-di-iodobutane, 1, 4-dibromobutane or 1, 4-dichlorobutane; the carbonate is selected from any one of potassium carbonate, sodium carbonate and magnesium carbonate; The aprotic polar organic solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran; The inert gas is selected from nitrogen or argon, In the step (2), the anhydrous aprotic polar organic solvent is selected from any one of anhydrous N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran; the amount of the n-butyllithium substance is 2-4 times of the product of the step 1; The full stirring time is 40-60 min; the 1, 2-dihalogen substituted tetrachloroethane is selected from 1, 2-dibromotetrachloroethane, 1, 2-dichloro tetrachloroethane or 1, 2-diiodotetrachloroethane; the low temperature reaction temperature was-75 ℃ and the reaction time was 1 h.
  5. 5. The method for preparing the dynamic optical switch molecule containing the endogenous chirality and the exogenous chirality according to claim 3, wherein: in the step (3), the molar ratio of the product of the step (2), potassium acetate, X-Phos, xphos Pd G, and methanol is 1:3:0.01:0.005:50, In step (4), BBTE-2 halogen substituents are selected from BBTE-2Cl or BBTE-2Br; The aprotic polar organic solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran; the carbonate is selected from any one of potassium carbonate, sodium carbonate and magnesium carbonate, and the concentration is 2 mol/L; reflux reaction time at 75 ℃ was 8h.
  6. 6. The method for preparing a dynamic optical switch molecule containing endogenous chirality and exogenous chirality according to claim 3, The method is characterized by further comprising a chiral resolution step, wherein the chiral resolution column is CHIRALPAK IC, the mobile phase is Hexane/DCM/DEA=60/40/0.1, the flow rate is 1.0ml/min, the wavelength of a detection light source is 254nm, and a pair of diastereoisomers are formed after resolution.
  7. 7. Use of a dynamic optical switch molecule containing an endogenous chirality and an exogenous chirality according to claim 1 or 2 for the preparation of a liquid crystal material.
  8. 8. A liquid crystal material comprising the dynamic optical switching molecule of claim 1 or 2 having an endogenous chirality and an exogenous chirality.
  9. 9. The method for preparing a liquid crystal material according to claim 8, wherein the liquid crystal material is formed by mixing 98-99 wt% of dynamic optical switch molecules containing endogenous chirality and exogenous chirality with liquid crystal TEB 300 for nematic consult according to a proportion of 1-2 wt% after chiral resolution.
  10. 10. A liquid crystal device comprising the liquid crystal material according to claim 8.

Description

Synthesis of chiral photochromic dye containing endogenous and exogenous and liquid crystal application thereof Technical Field The invention belongs to the field of photochromic dyes, relates to preparation and application of an endogenous and exogenous chiral optical switch, and in particular relates to preparation and application of an internal and external source chiral dynamic optical switch based on steric hindrance diaryl ethylene. Background The conventional diarylethene open ring body generates a pair of racemates after ring closure due to the rapid rotation of the side chain, so that the conventional diarylethene generally realizes chiral regulation by modifying additional chiral groups. However, the exo-chiral groups often produce an asymmetric inducing effect in the photocyclization reaction, forming a pair of diastereomers with opposite chiral centers, which are difficult to use for subsequent studies by chiral separation. The steric-type diaryl ethylene adopts benzodithiadiazole as an alkene bridge and benzothiophene as a side chain aryl. Due to the steric hindrance of the side chain benzothiophene, not only the parallel and antiparallel isomers p-BBTE and ap-BBTE can be isolated. The chiral isomers P-ap-BBTE and M-ap-BBTE can be further separated by further resolution of the chiral column, and the corresponding chiral isomers of the closed ring are respectively marked as (R, R) -c-BBTE and (S, S) -c-BBTE, which are light-responsive endogenous chiral switches with excellent thermal stability and fatigue resistance. In recent years, research on endogenous chirality and exogenous chirality is not proved, but few researches have interaction between the endogenous chirality and exogenous chiral materials, and the research on the aspects has a large blank, so that the research on stimulus-responsive optical switch molecules containing interaction between different types of chiral molecules has important significance. Disclosure of Invention The invention aims at the problems and provides a photochromic dye containing both endogenous chirality and exogenous chirality, which realizes a dynamic optical switch through interaction between the endogenous chirality and the exogenous chirality. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: In a first aspect of the invention, there is provided a class of dynamic optical switch molecules comprising endogenous chirality and exogenous chirality. The invention takes the steric type diaryl ethylene as a matrix, integrates the endogenous chirality and the exogenous chirality into a single molecule for the first time, and provides an internal and external source chiral dynamic optical switch based on the steric type diaryl ethylene. From the determination of whether binaphthol is bridged or not, the bridging length of binaphthol is changed, and the three side chain alkyl groups are introduced to change the molecular structure, the provided internal and external source chiral dynamic optical switch based on the steric hindrance diaryl ethylene has the structural general formula shown in the following formula I: (I) in formula I, n=0, 1,2, 3 or 4, R 1, R2, R3, R4 is selected fromAny one of them. The preferred structure is as follows: 。 endogenous chiralities P and M of the ap-RBNBT series molecule cancel each other, exogenous chiral R-binaphthol still exists, and the whole ap-RBNBT series molecule still has chiral characteristics. In a second aspect, the invention provides a synthesis method of the dynamic optical switch RBNBT series molecules containing the endogenous chirality and the exogenous chirality, which comprises the following synthesis route: the preparation method comprises the following specific steps: (1) Adding R-binaphthol and 1, 4-dibutyl halogen substituent in a molar ratio of 1:2-6 into a reaction container dried at high temperature (such as flame), then adding carbonate and aprotic polar organic solvent, and separating by silica gel column chromatography after complete reflux reaction at 80 ℃ under the protection of inert gas to obtain light yellow solid; (2) Adding the product obtained in the step (1) and the anhydrous aprotic polar organic solvent into a reaction vessel which is dried at a high temperature, cooling to-79 ℃, slowly adding n-butyllithium, fully stirring for a certain time, adding 1, 2-dihalogen substituted tetrachloroethane dissolved by the same aprotic polar organic solvent, wherein the amount of the substances is 1-4 times that of the product obtained in the step 1, completely reacting at a low temperature, shifting to room temperature, adding a small amount of water quenched butyllithium after the point plate monitoring reaction is complete, and separating by silica gel column chromatography to obtain white solid; (3) Adding the product obtained in the step (2) and tetrahydroxy diboron into a three-mouth bottle which is dried at high temperature according to the mol ratio o