CN113024375A - Preparation method of trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexane liquid crystal monomer - Google Patents
Preparation method of trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexane liquid crystal monomer Download PDFInfo
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Abstract
The application relates to the technical field of liquid crystal display material synthesis, and particularly discloses a preparation method of a trans, trans-4-alkyl-4 ' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer, which takes trans, trans-4-alkyl-4 ' -formic acid-bicyclohexyl and alkyl alcohol as starting materials and sequentially carries out esterification reaction, reduction reaction, acylation reaction and cross-coupling reaction to prepare the trans, trans-4-alkyl-4 ' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer. The method has the advantages of short synthetic route and low production cost, and is suitable for industrial production.
Description
Technical Field
The application relates to the technical field of liquid crystal display material synthesis, in particular to a preparation method of a trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer.
Background
Conversely, the trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexane liquid crystal monomer has the advantages of small viscosity, high response speed, good optical anisotropy, high compatibility with other liquid crystal monomers and the like, and meanwhile, the liquid crystal monomer has high clearing point and good tolerance to light and heat. Conversely, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexane liquid crystal monomers are used in a large amount in mixed crystals as a very important liquid crystal base material.
The prior patent document with the publication number of CN106753423B and publication date of 2018, 11 and 13 discloses a preparation method of a trans, trans-4-alkyl-4 '-pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer, which takes trans-4' -alkyl bicyclohexyl-4-ketone as an initiator and sequentially carries out six-step reactions such as Grignard reaction, hydrogenation reaction, deprotection reaction, isomerization, Wittig reaction, isomerization reaction and the like to obtain a target product.
The above preparation method has the following disadvantages: firstly, the synthesis steps are long, the total yield is low, and the industrial production is not facilitated; second, the hydrogenation reaction requires special equipment and has a physical and chemical explosion hazard, and deprotection substances are easily generated during the hydrogenation reaction, and the deprotection substances can be further reduced to generate harmful impurities.
Disclosure of Invention
In order to simplify the synthetic route, reduce the production cost and be suitable for industrial production, the application provides a preparation method of a trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer, which adopts the following technical scheme:
a preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexyl liquid crystal monomer comprises the following steps:
(i) adding trans, trans-4-alkyl-4' -formic acid-bicyclohexyl and alkyl alcohol in the molar ratio of 1 (20-25) into an organic solvent I at the temperature of 110 ℃ and 120 ℃, and carrying out a catalytic esterification reaction by concentrated sulfuric acid to generate a compound I, wherein the structural general formula of the compound I is
R1Is C1-C7 alkyl, R2Is C1-C4 alkyl;
(ii) under the condition of inert atmosphere and 55-65 ℃, the compound I with the molar ratio of 1 (1.3-2) to (1.3-2), potassium borohydride and lithium chloride are subjected to reduction reaction in an organic solvent II to generate a compound II, and the structural general formula of the compound II is shown in the specification
R1Is C1-C7 alkyl;
(iii) under the conditions of inert atmosphere and 0-5 ℃, dropwise adding a mixture containing tosyl chloride and an organic solvent III into a mixture containing a compound II, a binding agent, an acylation catalyst and the organic solvent III, heating to 20-30 ℃ after dropwise adding to generate an acylation reaction to generate a compound III, wherein the structural general formula of the compound III is
R1Is C1-C7 alkyl; the mol ratio of the compound II, the binding agent, the acylation catalyst and the paratoluensulfonyl chloride is 1 (1.1-1.5): (0.008-0.020): 1-1.1);
(iv) adding a Grignard reagent prepared from magnesium and 1-halogen-2-butene into a mixture of a compound III, a diene ligand catalyst and an organic solvent IV at the temperature of-30 ℃ and in an inert atmosphere, controlling the temperature to be 30-40 ℃, reacting for 3-6 hours, neutralizing a reaction system, and purifying to obtain the trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer, wherein the structural general formula is
R1Is C1-C7 alkyl; said combination ofThe molar ratio of the compound III, the diene ligand catalyst, the magnesium and the 1-halogen-2-butylene is 1 (0.04-0.1) to (1.7-2.1) to (1-1.5).
Preferably, the alkyl alcohol comprises at least one of methanol, ethanol, n-propanol and n-butanol.
Preferably, the organic solvent I is toluene.
Preferably, the weight ratio of the alkyl alcohol to the organic solvent I is 1 (4-8).
Preferably, the organic solvent II is tetrahydrofuran.
Preferably, the binding agent comprises at least one of pyridine, triethylamine and diisopropylethylamine, and the acylation catalyst is 4-dimethylaminopyridine.
Preferably, the organic solvent III is dichloromethane.
Preferably, the diene ligand catalyst is at least one selected from the group consisting of nickel diallyl oxide and palladium diallyl oxide.
Preferably, the 1-halo-2-butene comprises at least one of 1-chloro-2-butene and 1-bromo-2-butene.
Preferably, the organic solvent IV is tetrahydrofuran.
In summary, the present application has the following beneficial effects:
first, the method simplifies the synthetic route, reduces the production cost, and is suitable for industrial production.
Secondly, the application adopts bis-allylnickel or bis-allylpalladium as a catalyst in the step (iv), so that higher yield can be obtained and the purity of the target product is higher when the coupling reaction of the compound III and the 1-chloro-2-butene Grignard reagent is catalyzed. However, when dilithium tetrachlorocuprate is used as a catalyst, the yield and purity of the obtained target product are not ideal, because the carbon-carbon double bond in the Grignard reagent influences the cross coupling reaction, promotes the occurrence of side reaction and influences the yield and purity of the target product.
Detailed Description
The present application will be described in further detail with reference to examples.
A synthetic route of a trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer is as follows:
the trans, trans-4-alkyl-4 '-amyl-3 (E) alkene-bicyclohexyl liquid crystal monomer is prepared by taking trans, trans-4-alkyl-4' -formic acid-bicyclohexyl as an initiator and sequentially carrying out esterification reaction, reduction reaction, acylation reaction and cross-coupling reaction.
Example 1
When R is1When the target product is n-propyl, the target product is trans, trans-4-n-propyl-4' -pentyl-3 (E) ene-bicyclohexane.
Synthesis of Compound I: adding 80g of toluene and 320g of methanol into a 1L three-necked bottle, then adding 80g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexyl, slowly adding 8g of concentrated sulfuric acid, and carrying out reflux reaction for 3 hours; methanol is evaporated by rotary evaporation, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice with water, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration to obtain 84.5g of the compound I with the yield of 100%.
Synthesis of Compound II: 400g of tetrahydrofuran and 84.5g (0.316mol) of compound I were charged into a 1L three-necked flask, 27.1g (0.475mol) of potassium borohydride and 20.1g (0.475mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the temperature was controlled at 60 ℃ for reaction for 5 hours, and the reaction was monitored by GC to be completed.
Cooling to room temperature, neutralizing the reaction system with 10 wt% hydrochloric acid, extracting with 140g of toluene, standing, separating, extracting the lower aqueous phase with 70g of toluene, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating the dry solvent under negative pressure to obtain 75.6g of compound II with a yield of 100%.
Synthesis of Compound III: adding 300g of dichloromethane and 75.6g of compound II into a 1L three-necked bottle, then adding 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine, cooling to 0 ℃ under the protection of nitrogen, dropwise adding 63.2g of dichloromethane (250mL) solution of p-toluenesulfonyl chloride, heating to 25 ℃ after dropwise adding, continuing to react for 10 hours, and monitoring by HPLC to finish the reaction.
160g of water was added to the reaction system, and the mixture was stirred for 10 minutes, allowed to stand for liquid separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, 330g of n-heptane was added thereto, the temperature was raised to 60 ℃, stirred for 1 hour, cooled to 0 ℃, filtered and dried to obtain white compound III, 116.3g, yield 93.5% (without mother liquor recovery).
And (3) synthesis of a target product: adding 13.8g (0.57mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran into a 500mL three-necked bottle under the protection of nitrogen, preparing a tetrahydrofuran (105mL) solution of 34.8g (0.38mol) of 1-chloro-2-butene, controlling the temperature to be 0-20 ℃, dropwise adding the tetrahydrofuran solution of 1-chloro-2-butene into the three-necked bottle, and preserving the temperature for 1 hour after the dropwise adding is finished to react to obtain the Grignard reagent.
Adding 620g of tetrahydrofuran, 116.3g (0.30mol) of the compound III and nitrogen protection into a 2L three-necked bottle, cooling to-30 ℃, adding 30mL of 1mol/L n-hexane solution of bis (allylnickel) into the bottle, dropwise adding the Grignard reagent, and after dropwise adding, preserving heat and reacting for 3 hours. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
And extracting with n-heptane after quenching, washing an organic phase with water to be neutral, drying with anhydrous sodium sulfate, concentrating under reduced pressure to evaporate the solvent, recrystallizing for three times by adopting an n-heptane/ethanol system with the volume ratio of 1:4, and drying to obtain a target product of 68.8g, the purity of 99.9 percent and the yield of 73 percent.
Characterization of the target product:
1H-NMR(400MHz,CDCl3)：δ:5.34-5.45(m,2H)；1.95-1.99(m,2H)；1.67-1.75(q,8H)；1.62-1.64(m, 3H)；1.10-1.30(m,8H)；0.93-0.99(m,6H)；0.84-0.88(t,7H)；
MS：m/z 276(M+)。
example 2
When R is1In the case of ethyl, the desired product is trans, trans-4-ethyl-4' -pentyl-3 (E) ene-bicyclohexane.
Synthesis of Compound I: adding 80g of toluene and 320g of methanol into a 1L three-necked bottle, then adding 75.65g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexyl, slowly adding 8g of concentrated sulfuric acid, and carrying out reflux reaction for 3 hours; methanol is evaporated by rotary evaporation, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice with water, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration to obtain 80.1g of the compound I with the yield of 100%.
Synthesis of Compound II: 400g of tetrahydrofuran and 79.85g (0.316mol) of compound I were charged into a 1L three-necked flask, 27.1g (0.475mol) of potassium borohydride and 20.1g (0.475mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the temperature was controlled at 60 ℃ for reaction for 5 hours, and the reaction was monitored by GC to be completed.
Cooling to room temperature, neutralizing the reaction system with 10 wt% hydrochloric acid, extracting with 140g of toluene, standing, separating, extracting the lower aqueous phase with 70g of toluene, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating the dry solvent under negative pressure to obtain 71.0g of compound II with the yield of 100%.
Synthesis of Compound III: adding 300g of dichloromethane and 71.0g of compound II into a 1L three-necked bottle, then adding 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine, cooling to 0 ℃ under the protection of nitrogen, dropwise adding 63.2g of dichloromethane (250mL) solution of p-toluenesulfonyl chloride, heating to 25 ℃ after dropwise adding, continuing to react for 10 hours, and monitoring by HPLC to finish the reaction.
160g of water was added to the reaction system, and the mixture was stirred for 10 minutes, allowed to stand for liquid separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, to which was added 330g of n-heptane, heated to 60 ℃, stirred for 1 hour, cooled to 0 ℃, filtered and dried to obtain 113.49g of white compound III, with a yield of 95.3% (without mother liquor recovery).
And (3) synthesis of a target product: adding 13.8g (0.57mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran into a 500mL three-necked bottle under the protection of nitrogen, preparing a tetrahydrofuran (105mL) solution of 34.8g (0.38mol) of 1-chloro-2-butene, controlling the temperature to be 0-20 ℃, dropwise adding the tetrahydrofuran solution of 1-chloro-2-butene into the three-necked bottle, and preserving the temperature for 1 hour after the dropwise adding is finished to react to obtain the Grignard reagent.
Adding 620g of tetrahydrofuran, 113.05g (0.30mol) of compound III and nitrogen protection into a 2L three-necked bottle, cooling to-30 ℃, adding 30mL of 1mol/L n-hexane solution of bis (allylnickel) into the bottle, dropwise adding the Grignard reagent, and after dropwise adding, preserving heat and reacting for 3 hours. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
And extracting with n-heptane after quenching, washing an organic phase with water to be neutral, drying with anhydrous sodium sulfate, concentrating under reduced pressure to evaporate the solvent, recrystallizing for three times by adopting an n-heptane/ethanol system with the volume ratio of 1:4, and drying to obtain 59.1g of a target product with the purity of 99.9% and the yield of 75%.
Characterization of the target product:
1H-NMR(400MHz,CDCl3)：δ:5.44(2H,m)；2.05(2H,m)；1.64(3H,m)；1.35～1.61(14H,m)； 1.12～1.30(10H,m)；0.88(3H,m)；
MS,m/z 262(M+)。
example 3
When R is1In the case of n-pentyl, the desired product is trans, trans-4-n-pentyl-4' -pentyl-3 (E) ene-bicyclohexane.
Synthesis of Compound I: adding 80g of toluene and 320g of methanol into a 1L three-necked bottle, then adding 88g of trans, trans-4-n-propyl-4' -formic acid-bicyclohexyl, slowly adding 8g of concentrated sulfuric acid, and carrying out reflux reaction for 3 hours; methanol is evaporated by rotary evaporation, the temperature is reduced to 40 ℃, 80g of toluene is added, the mixture is washed twice with water, dried by anhydrous sodium sulfate, and the solvent is evaporated by decompression concentration to obtain 92.4g of the compound I with the yield of 100%.
Synthesis of Compound II: 400g of tetrahydrofuran and 93.1g (0.316mol) of compound I were charged into a 1L three-necked flask, 27.1g (0.475mol) of potassium borohydride and 20.1g (0.475mol) of anhydrous lithium chloride were added under stirring, the mixture was replaced with nitrogen, the temperature was controlled at 60 ℃ for reaction for 5 hours, and the reaction was monitored by GC to be completed.
Cooling to room temperature, neutralizing the reaction system with 10 wt% hydrochloric acid, extracting with 140g of toluene, standing, separating, extracting the lower aqueous phase with 70g of toluene, combining the organic phases, drying with anhydrous sodium sulfate, and concentrating the dry solvent under negative pressure to obtain 84.2g of compound II with the yield of 100%.
Synthesis of Compound III: adding 300g of dichloromethane and 84.2g of compound II into a 1L three-necked bottle, then adding 41.6g of triethylamine and 0.38g of 4-dimethylaminopyridine, cooling to 0 ℃ under the protection of nitrogen, dropwise adding 63.2g of dichloromethane (250mL) solution of p-toluenesulfonyl chloride, heating to 25 ℃ after dropwise adding, continuing to react for 10 hours, and monitoring by HPLC to finish the reaction.
160g of water was added to the reaction system, and the mixture was stirred for 10 minutes, allowed to stand for liquid separation, the aqueous phase was extracted with 100g of methylene chloride, the organic phases were combined, washed twice with water, and dried over anhydrous sodium sulfate. The dried organic phase was concentrated to dryness, 330g of n-heptane was added thereto, the temperature was raised to 60 ℃, stirred for 1 hour, cooled to 0 ℃, filtered and dried to obtain white compound III, 122.0g, yield 92.2% (without mother liquor recovery).
And (3) synthesis of a target product: adding 13.8g (0.57mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran into a 500mL three-necked bottle under the protection of nitrogen, preparing a tetrahydrofuran (105mL) solution of 34.8g (0.38mol) of 1-chloro-2-butene, controlling the temperature to be 0-20 ℃, dropwise adding the tetrahydrofuran solution of 1-chloro-2-butene into the three-necked bottle, and preserving the temperature for 1 hour after the dropwise adding is finished to react to obtain the Grignard reagent.
Adding 620g of tetrahydrofuran, 125.6g (0.30mol) of the compound III and nitrogen protection into a 2L three-necked bottle, cooling to-30 ℃, adding 30mL of 1mol/L n-hexane solution of bis (allylnickel) into the bottle, dropwise adding the Grignard reagent, and after dropwise adding, preserving heat and reacting for 3 hours. After the reaction is finished, hydrochloric acid with the weight percentage concentration of 10% is slowly dripped to neutralize the reaction system so as to quench the reaction.
And extracting with n-heptane after quenching, washing an organic phase with water to be neutral, drying with anhydrous sodium sulfate, concentrating under reduced pressure to evaporate the solvent, recrystallizing for three times by adopting an n-heptane/ethanol system with the volume ratio of 1:4, and drying to obtain a target product of 65.8g, the purity of 99.9 percent and the yield of 72 percent.
Characterization of the target product:
1H-NMR(400MHz,CDCl3)：δ:5.43(2H,m)；2.07(2H,m)；1.47-1.63(11H,m)；1.15-1.45(18H,m)； 1.00(2H,m)；0.89(3H,m)；
MS,m/z 290(M+)。
comparative example 1
When R is1When the target product is n-propyl, the target product is trans, trans-4-n-propyl-4' -pentyl-3 (E) ene-bicyclohexane.
And (3) synthesis of a target product: the same as example 1 except that the catalyst bis (allylnickel) was replaced with dilithium tetrachlorocuprate.
The specific synthesis steps are as follows: adding 13.8g (0.57mol) of magnesium chips and 30mL of anhydrous tetrahydrofuran into a 500mL three-necked bottle, preparing a tetrahydrofuran (105mL) solution of 34.8g (0.38mol) of 1-chloro-2-butene, controlling the temperature to be 0-20 ℃, dropwise adding the tetrahydrofuran solution of 1-chloro-2-butene into the three-necked bottle, and after dropwise adding, carrying out heat preservation reaction for 1 hour to obtain the Grignard reagent.
620g of tetrahydrofuran, 116.3g (0.30mol) of the compound III and 80mL of 0.2mol/L dilithium tetrachlorocuprate solution are added into a 2L three-necked flask, the temperature is reduced to 0 ℃ under the protection of nitrogen, the Grignard reagent is added dropwise, and the temperature is increased to 25 ℃ after the addition of the Grignard reagent, so as to react for 12 hours. After the reaction is finished, the temperature is reduced to 0 ℃, hydrochloric acid with the weight percentage concentration of 10% is slowly dropped to neutralize the reaction system, so that the reaction is quenched.
After quenching, extracting with n-heptane, washing an organic phase with water to be neutral, drying with anhydrous sodium sulfate, concentrating under reduced pressure to evaporate the solvent, recrystallizing for three times by adopting an n-heptane/ethanol system with the volume ratio of 1:4, and drying to obtain 49.0g of a target product with the purity of 97.2% and the yield of 52%.
By combining example 1 and comparative example 2, the cross-coupling reaction of bis-allylnickel catalytic compound III and Grignard reagent prepared from magnesium and 1-chloro-2-butene can be realized with high yield and high purity of the target product. However, the yield and purity of the target product obtained by using the lithium tetrachlorocuprate to catalyze the cross-coupling reaction of the compound III and the Grignard reagent prepared from magnesium and 1-chloro-2-butene are not ideal, because the carbon-carbon double bond in the Grignard reagent affects the cross-coupling reaction, promotes the occurrence of side reactions, and affects the yield and purity of the target product.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexyl liquid crystal monomer is characterized by comprising the following steps:
(i) adding trans, trans-4-alkyl-4' -formic acid-bicyclohexyl and alkyl alcohol in the molar ratio of 1 (20-25) into an organic solvent I at the temperature of 110 ℃ and 120 ℃, and carrying out a catalytic esterification reaction by concentrated sulfuric acid to generate a compound I, wherein the structural general formula of the compound I is
R1Is C1-C7 alkyl, R2Is C1-C4 alkyl;
(ii) under the condition of inert atmosphere and 55-65 ℃, the compound I with the molar ratio of 1 (1.3-2) to (1.3-2), potassium borohydride and lithium chloride are subjected to reduction reaction in an organic solvent II to generate a compound II, and the structural general formula of the compound II is shown in the specification
R1Is C1-C7 alkyl;
(iii) under the conditions of inert atmosphere and 0-5 ℃, dropwise adding a mixture containing tosyl chloride and an organic solvent III into a mixture containing a compound II, a binding agent, an acylation catalyst and the organic solvent III, heating to 20-30 ℃ after dropwise adding to generate an acylation reaction to generate a compound III, wherein the structural general formula of the compound III is
R1Is C1-C7 alkyl; the mol ratio of the compound II, the binding agent, the acylation catalyst and the paratoluensulfonyl chloride is 1 (1.1-1.5): (0.008-0.020): 1-1.1);
(iv) adding a Grignard reagent prepared from magnesium and 1-halogen-2-butene into a mixture of a compound III, a diene ligand catalyst and an organic solvent IV at the temperature of-30 ℃ and in an inert atmosphere, controlling the temperature to be 30-40 ℃, reacting for 3-6 hours, neutralizing a reaction system, and purifying to obtain the trans, trans-4-alkyl-4' -pentyl-3 (E) ene-bicyclohexyl liquid crystal monomer, wherein the structural general formula is
R1Is C1-C7 alkyl; the mol ratio of the compound III, the diene ligand catalyst, the magnesium and the 1-halogen-2-butylene is 1 (0.04-0.1) to (1.7-2.1) to (1-1.5).
2. The method according to claim 1, wherein the alkyl alcohol comprises at least one of methanol, ethanol, n-propanol and n-butanol.
3. The method according to claim 1, wherein the organic solvent I is toluene.
4. The method according to claim 1, wherein the weight ratio of the alkyl alcohol to the organic solvent I is 1 (4-8).
5. The method according to claim 1, wherein the organic solvent II is tetrahydrofuran.
6. The method of claim 1, wherein the binding agent comprises at least one of pyridine, triethylamine, and diisopropylethylamine, and the acylation catalyst is 4-dimethylaminopyridine.
7. The method according to claim 1, wherein the organic solvent III is dichloromethane.
8. The preparation method according to claim 1, wherein the diene ligand catalyst is at least one selected from the group consisting of bis-allylnickel and bis-allylpalladium.
9. The method according to claim 1, wherein the 1-halo-2-butene comprises at least one of 1-chloro-2-butene and 1-bromo-2-butene.
10. The method according to claim 1, wherein the organic solvent IV is tetrahydrofuran.
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