CN112279760B - Etherification method of cyclohexyl alcohol compound - Google Patents
Etherification method of cyclohexyl alcohol compound Download PDFInfo
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- CN112279760B CN112279760B CN202011186188.5A CN202011186188A CN112279760B CN 112279760 B CN112279760 B CN 112279760B CN 202011186188 A CN202011186188 A CN 202011186188A CN 112279760 B CN112279760 B CN 112279760B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/188—Unsaturated ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/08—Saturated compounds containing ether groups, groups, groups, or groups
- C07C62/10—Saturated compounds containing ether groups, groups, groups, or groups with a six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The method uses cyclohexyl alcohol compound and halohydrocarbon as raw materials, and carries out etherification reaction in the presence of a composite phase transfer catalyst, wherein the composite phase transfer catalyst comprises a quaternary ammonium salt phase transfer catalyst and a cyclic crown ether phase transfer catalyst. The etherification reaction has not only a purity of not less than 99% but also a yield of not less than 95%.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials; relates to an etherification method of a liquid crystal compound, in particular to an etherification method of a cyclohexyl alcohol compound.
Background
Liquid crystal displays using a liquid crystal composition are widely used in displays of instruments, computers, televisions and the like, and the liquid crystal composition plays an important role in improving the performance of the liquid crystal display as one of important optoelectronic materials of the liquid crystal display. At present, a large number of liquid crystal compounds with different molecular structures appear in the market, and the liquid crystal compounds are developed from biphenyl nitrile, esters, oxygen-containing heterocyclic ring liquid crystal compounds to cyclohexylbenzene, phenylacetylene, ethyl bridge, alkenyl-terminated liquid crystal, various fluorine-containing aromatic ring liquid crystal compounds and the like, so that the performance requirements of TN, STN, TFT-LCD and other displays are continuously met.
A great deal of liquid crystals are synthesized by introducing cyclohexane skeleton structures into main chains or side chains of liquid crystal compounds. The cyclohexane structure is introduced into the molecule, so that the thermo-oxidative stability, chemical stability and optical stability of the liquid crystal compound can be obviously improved, and the mechanical property, dielectric property and other various properties of the liquid crystal compound are improved, so that a series of liquid crystal display materials with special functions are obtained.
In the liquid crystal monomers commonly used, the rigid structure of the molecule mostly contains 1 or more cyclohexane groups. Compared with the biphenyl liquid crystal widely used at present, the liquid crystal molecular structure containing 1 or more cyclohexane groups has the advantages of high phase transition temperature, small viscosity, high response speed and the like in the aspect of liquid crystal display performance, is an indispensable effective component in the formula of the medium-high grade mixed liquid crystal material, and therefore, the preparation method of the biphenyl liquid crystal has important value.
Among these, in order to obtain a compound having an ether bond in the side chain, the compound is usually obtained by etherification of a cyclohexyl alcohol compound.
The etherification reaction of the compounds in the prior art mainly comprises the following steps:
in the first category, sodium hydrogen strong alkali is used for high-temperature reflux in DMF to directly obtain the product.
Such methods utilize SN 2 The principle of nucleophilic substitution requires that the protons on the alcoholic hydroxyl groups of the cyclohexyl alcohol be pulled down by a strong base, while the reaction is carried out in aprotic solvent (usually DMF). The reaction is simple, but because sodium hydrogen is used as strong alkali, the requirement on the water content of the solvent is more severe, strict water removal is needed, and the industrial production is not facilitated.
And secondly, using phenol to etherify firstly, and then hydrogenating and reducing benzene rings to obtain a final product.
The method adopts corresponding substituted phenol to carry out etherification reaction, reduces the requirements on alkali and solvent, and is easy to realize industrialization; but high-temperature high-pressure hydrogenation is needed, the steps are long, the yield is low, and the cost is high.
Third, dhiraj O.Katola et al use tetrabutylammonium bromide as a phase transfer catalyst for phase transfer catalytic reactions. The method has the advantages of short steps, high yield, mild reaction conditions and less three wastes. However, there is still a technical disadvantage of low yield in the etherification reaction of cyclohexyl alcohol compounds.
Therefore, there is an urgent need to develop a method for etherification of cyclohexyl alcohol compounds with high purity and high yield in view of the above-mentioned technical drawbacks.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for etherifying a cyclohexyl alcohol compound with high purity and high yield. Compared with the prior art, the etherification reaction provided by the invention has purity not lower than 99% and yield not lower than 95%.
In order to achieve the purpose of the invention, the following technical scheme is adopted: the etherification method of the cyclohexyl alcohol compound takes the cyclohexyl alcohol compound and the halohydrocarbon as raw materials and carries out etherification reaction in the presence of a composite phase transfer catalyst, and is characterized in that the composite phase transfer catalyst comprises a quaternary ammonium salt phase transfer catalyst and a cyclic crown ether phase transfer catalyst.
The etherification process according to the present invention, wherein the quaternary ammonium salt phase transfer catalyst is selected from one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, benzyltriethylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride.
Preferably, the quaternary ammonium salt phase transfer catalyst is selected from tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium chloride.
In a specific embodiment, the quaternary ammonium salt phase transfer catalyst is selected from tetrabutylammonium bromide.
The etherification process according to the present invention wherein the cyclic crown ether phase transfer catalyst is selected from the group consisting of 18-crown ether-6, 15-crown ether-5, 12-crown ether-4 and α, β, γ -cyclodextrin.
Preferably, the cyclic crown ether phase transfer catalyst is selected from the group consisting of 18-crown ether-6, 15-crown ether-5, 12-crown ether-4.
In a specific embodiment, the cyclic crown ether phase transfer catalyst is selected from 18-crown ether-6.
The etherification method provided by the invention is characterized in that the general structure of the cyclohexyl alcohol compound is as follows:
wherein R is selected from carboxyl, ester group, cyclohexyl or substituted cyclohexyl, phenyl or substituted phenyl.
Preferably, R is selected from carboxyl, phenyl or substituted phenyl.
In a specific embodiment, R is selected from carboxyl.
As substituents on cyclohexyl or phenyl, the substituents being C 1 -C 20 Straight-chain alkyl or straight-chain alkoxy of (C) 1 -C 20 A linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl group.
Preferably, the substituent is C 1 -C 10 Straight-chain alkyl or straight-chain alkoxy of (C) 1 -C 10 A linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl group;
more preferably, the substituent is C 1 -C 6 Straight-chain alkyl or straight-chain alkoxy of (C) 1 -C 6 A linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl group;
and, most preferably, the substituent is C 1 -C 4 Straight-chain alkyl or straight-chain alkoxy of (C) 1 -C 4 A linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl group.
In a specific embodiment, the substituent is C 1 -C 4 Straight chain alkyl of (a).
On the other hand, the substitution position as a substituent on R and cyclohexyl or phenyl is advantageously in the para position.
The etherification method according to the present invention, wherein the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: (1.01-1.4).
Preferably, the molar ratio of cyclohexyl alcohol compound to halogenated hydrocarbon is 1: (1.02-1.3); more preferably, the molar ratio of cyclohexyl alcohol compound to halogenated hydrocarbon is 1: (1.03-1.2); and, most preferably, the molar ratio of cyclohexyl alcohol compound to halogenated hydrocarbon is 1: (1.04-1.1).
In a specific embodiment, the molar ratio of cyclohexyl alcohol compound to halogenated hydrocarbon is 1:1.05.
the etherification process according to the present invention, wherein the quaternary ammonium salt phase transfer catalyst is added in an amount of 1 to 10mol% based on the number of moles of the cyclohexyl alcohol compound.
Preferably, the quaternary ammonium salt phase transfer catalyst is added in an amount of 2 to 8mol% based on the number of moles of the cyclohexyl alcohol compound; more preferably, the quaternary ammonium salt phase transfer catalyst is added in an amount of 3 to 7mol% based on the number of moles of the cyclohexyl alcohol compound; and, most preferably, the quaternary ammonium salt phase transfer catalyst is added in an amount of 4 to 6 mole% based on the moles of the cyclohexyl alcohol compound.
In a specific embodiment, the quaternary ammonium salt phase transfer catalyst is added in an amount of 5 mole percent based on moles of cyclohexyl alcohol compound.
The etherification process according to the present invention, wherein the cyclic crown ether phase transfer catalyst is added in an amount of 0.4 to 2.4mol% based on the number of moles of the cyclohexyl alcohol compound.
Preferably, the cyclic crown ether phase transfer catalyst is added in an amount of 0.6 to 2.1 mole% based on the moles of the cyclohexyl alcohol compound; more preferably, the cyclic crown ether phase transfer catalyst is added in an amount of 0.8 to 1.8 mole% based on the moles of the cyclohexyl alcohol compound; and, most preferably, the cyclic crown ether phase transfer catalyst is added in an amount of 1 to 1.5 mole% based on the moles of the cyclohexyl alcohol compound.
In a specific embodiment, the cyclic crown ether phase transfer catalyst is added in an amount of 1.2 mole percent based on moles of cyclohexyl alcohol compound.
The etherification process according to the present invention, wherein the composite phase transfer catalyst further comprises potassium iodide.
The etherification process according to the present invention, wherein potassium iodide is added in an amount of 1 to 10mol% based on the number of moles of the cyclohexyl alcohol compound.
Preferably, potassium iodide is added in an amount of 2 to 8mol% based on the number of moles of the cyclohexyl alcohol compound; more preferably, the potassium iodide is added in an amount of 3 to 7mol% based on the mole number of the cyclohexyl alcohol compound; and, most preferably, potassium iodide is added in an amount of 4 to 6mol% based on the number of moles of the cyclohexyl alcohol compound.
In a specific embodiment, potassium iodide is added in an amount of 5 mole percent based on moles of cyclohexyl alcohol compound.
The etherification method according to the present invention, wherein the temperature of the etherification reaction is 30 to 100 ℃.
Preferably, the temperature of the etherification reaction is 40-98 ℃; more preferably, the temperature of the etherification reaction is 50-95 ℃; and, most preferably, the temperature of the etherification reaction is 60-90 ℃.
In a specific embodiment, the etherification reaction temperature is 70 ℃.
Advantageously, tetrahydrofuran and water are used as solvents for the etherification reaction.
The etherification method of the invention takes cyclohexyl alcohol compounds and halogenated hydrocarbons as raw materials, and carries out etherification reaction in the presence of a composite phase transfer catalyst. The composite phase transfer catalyst comprises a quaternary ammonium salt phase transfer catalyst and a cyclic crown ether phase transfer catalyst. The inventors found that in the etherification reaction, especially when potassium iodide is further contained, the etherification reaction has not only a purity of not less than 99% but also a yield of not less than 95%.
The materials, compounds, compositions and components described herein may be used in, or in combination with, the methods and compositions described herein or may be used to practice and prepare the compositions or as products obtained by the methods. It is to be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each and every one of these compounds may not be explicitly contemplated and described herein. For example, if an extraction aid component is disclosed and discussed, and a number of alternative solid state forms of the component are discussed, each combination and permutation of the aid component and the solid state forms that are possible are specifically contemplated unless specifically indicated to the contrary. This concept applies to all aspects of the invention including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a plurality of additional steps that can be performed, it should be understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated as being disclosed.
In this specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
it must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both a reference and a plurality of references (i.e., more than two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in the present invention are approximate, and thus values outside the ranges may be included. The numerical ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will also be understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
References in the specification and the claims to parts by weight of a particular element or component in a composition or article refer to the relationship by weight between that element or component and any other element or component in the composition or article.
All fractions and percentages mentioned in the present invention are by weight, unless specifically indicated to the contrary, or implied by the context of the context or conventional manner in the art, and the weight percentages of the components are based on the total weight of the composition or product comprising the components.
References to "comprising," "including," "having," and similar terms in this invention are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials. In contrast, the term "consisting of … …" excludes any component, step or procedure not specifically recited or enumerated. The term "or" refers to members recited individually as well as in any combination unless otherwise specified.
Furthermore, the contents of any of the referenced patent documents or non-patent documents in the present invention are incorporated by reference in their entirety, especially with respect to the definitions and general knowledge disclosed in the art (in case of not inconsistent with any definitions specifically provided by the present invention).
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods described and claimed herein are made and evaluated, and are intended to be merely exemplary and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for.
Unless otherwise indicated, parts are parts by weight, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
In the present invention, the product content or ratio is determined by gas chromatography GC. The content unit is mol%.
Example 1
100ml of tetrahydrofuran is added into a three-port bottle, 50g of water is added, 10g of 4-hydroxycyclohexanecarboxylic acid is added, 9.38g of bromopropane is added, 1g of tetrabutylammonium bromide, 0.5g of potassium iodide and 0.2g of 18-crown ether-6 are added, reflux reaction is carried out for 24 hours at a temperature of 80 ℃, after the reaction is finished, a liquid separating water layer is recycled, the organic phase is distilled to recycle tetrahydrofuran, 50ml of isopropanol is added, crystallization is carried out, the product is filtered to 12.2g by suction, sampling is carried out, the GC is carried out, the purity is 99%, and the yield is 95%.
Example 2
100ml of tetrahydrofuran is added into a three-port bottle, 50g of water is added, 10g of raw material s-1 is added, 6.8g of bromopropane is added, 1g of tetrabutylammonium bromide is added, 0.5g of potassium iodide and 0.2g of 18-crown ether-6 are heated (70 ℃) to reflux for 24 hours, after the reaction is finished, a liquid separation water layer is recycled for reuse, an organic phase is distilled to recycle tetrahydrofuran, 50ml of isopropanol is added, crystallization is carried out, the product is filtered to 11.72g by suction, sampling and GC is carried out, the purity is 99%, and the yield is 96%.
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the invention, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
Claims (1)
1. The etherification method of the cyclohexyl alcohol compound comprises the following steps:
100ml of tetrahydrofuran is added into a three-port bottle, 50g of water is added, 10g of 4-hydroxycyclohexanecarboxylic acid is added, 9.38g of bromopropane is added, 1g of tetrabutylammonium bromide, 0.5g of potassium iodide and 0.2g of 18-crown ether-6 are added, reflux reaction is carried out for 24 hours at the temperature of 80 ℃, after the reaction is finished, a liquid separation water layer is recycled, the organic phase is distilled and recycled to tetrahydrofuran, 50ml of isopropanol is added, crystallization is carried out, the product is filtered to 12.2g by suction, sampling and GC is carried out, the purity is 99%, and the yield is 95%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220277A (en) * | 2007-12-04 | 2008-07-16 | 烟台万润精细化工股份有限公司 | Negative ester liquid crystal compound containing side direction difluorobenzene group and method for producing the same |
| CN101434520A (en) * | 2008-12-16 | 2009-05-20 | 淮海工学院 | Preparation of tetrabromobisphenol A diallyl ether |
| CN102050767A (en) * | 2009-11-11 | 2011-05-11 | 江苏傲伦达科技实业股份有限公司 | Preparation method of 1,1'-sulfonyl bis(4-(2-propylene)oxy benzene) |
| CN103788057A (en) * | 2014-02-28 | 2014-05-14 | 江苏省激素研究所股份有限公司 | Synthetic method for piperonyl butoxide |
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- 2020-10-29 CN CN202011186188.5A patent/CN112279760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220277A (en) * | 2007-12-04 | 2008-07-16 | 烟台万润精细化工股份有限公司 | Negative ester liquid crystal compound containing side direction difluorobenzene group and method for producing the same |
| CN101434520A (en) * | 2008-12-16 | 2009-05-20 | 淮海工学院 | Preparation of tetrabromobisphenol A diallyl ether |
| CN102050767A (en) * | 2009-11-11 | 2011-05-11 | 江苏傲伦达科技实业股份有限公司 | Preparation method of 1,1'-sulfonyl bis(4-(2-propylene)oxy benzene) |
| CN103788057A (en) * | 2014-02-28 | 2014-05-14 | 江苏省激素研究所股份有限公司 | Synthetic method for piperonyl butoxide |
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