CN112279760A - A kind of etherification method of cyclohexyl alcohol compound - Google Patents

A kind of etherification method of cyclohexyl alcohol compound Download PDF

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CN112279760A
CN112279760A CN202011186188.5A CN202011186188A CN112279760A CN 112279760 A CN112279760 A CN 112279760A CN 202011186188 A CN202011186188 A CN 202011186188A CN 112279760 A CN112279760 A CN 112279760A
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etherification
phase transfer
transfer catalyst
cyclohexyl alcohol
cyclohexyl
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CN112279760B (en
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郑飞翔
殷勇
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Jiangsu Creative Electronic Chemicals Co ltd
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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
    • 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
    • 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
    • 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
    • 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

公开了一种环己基醇类化合物的醚化方法，该方法以环己基醇类化合物和卤代烃作为原料，在复合相转移催化剂存在下进行醚化反应，复合相转移催化剂包含季铵盐类相转移催化剂和环状冠醚相转移催化剂。醚化反应不仅具有不低于99％的纯度，同时具有不低于95％的收率。Disclosed is a method for etherification of cyclohexyl alcohol compounds. The method uses 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 quaternary ammonium salts Phase transfer catalysts and cyclic crown ether phase transfer catalysts. The etherification reaction not only has a purity of not less than 99%, but also a yield of not less than 95%.

Description

Etherification method of cyclohexyl alcohol compound
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 the liquid crystal composition are widely used in displays such as 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. A large number of liquid crystal compounds with different molecular structures appear in the market at present, the liquid crystal compounds are developed from biphenylnitrile, esters, oxygen-containing heterocyclic rings and pyrimidine ring liquid crystal compounds to cyclohexylbenzene, phenylacetylene, ethyl bridges, terminal alkenyl liquid crystals, various fluorine-containing aromatic ring liquid crystal compounds and the like, and the performance requirements of displays such as TN, STN, TFT-LCD and the like are continuously met.
People have introduced cyclohexane skeleton structure into the main chain or side chain of liquid crystal compound to synthesize great amount of liquid crystal. The cyclohexane structure introduced into the molecules can obviously improve the thermal oxygen stability, the chemical stability and the optical stability of the liquid crystal compound, and improve the mechanical property, the dielectric property and other properties of the liquid crystal compound, thereby obtaining a series of liquid crystal display materials with special functions.
In the liquid-crystalline monomers usually used, the molecular rigidity structure mostly contains 1 or more cyclohexane groups. Compared with the biphenyl liquid crystal which is widely used at present, the liquid crystal molecular structure containing 1 or more cyclohexane groups has the advantages of high phase transition temperature, low viscosity, high response speed and the like on the aspect of liquid crystal display performance, and is an indispensable effective component in the formula of medium-high grade mixed liquid crystal materials, so that the preparation method of the liquid crystal molecular structure has important value.
Among these compounds, in order to further obtain a compound having an ether bond in a side chain, a cyclohexyl alcohol compound is generally subjected to etherification reaction.
The etherification reaction of the compounds in the prior art mainly comprises the following steps:
in the first category, sodium-hydrogen strong base is used for high-temperature reflux in DMF to directly obtain the product.
Figure BDA0002751454910000021
Such methods utilize SN2The nucleophilic substitution principle requires pulling down the proton from the alcoholic hydroxyl group of cyclohexyl alcohol by a strong base, while the reaction needs to be carried out in an aprotic solvent (usually DMF). Although the reaction is simple, the requirement on the water content of the solvent is severe due to the use of sodium hydrogen as strong alkali, strict dehydration is required, and the industrial production is not facilitated.
And secondly, etherifying phenol, and then hydrogenating and reducing a benzene ring to obtain a final product.
Figure BDA0002751454910000022
The method adopts corresponding substituted phenol for etherification reaction, reduces the requirements on alkali and solvent, and is easy to realize industrialization; but requires high-temperature high-pressure hydrogenation, and has the disadvantages of long steps, low yield and high cost.
The third category, Dhiraj o.katola et al, uses tetrabutylammonium bromide as a phase transfer catalyst for the phase transfer catalysis reaction. The method has the advantages of short steps, high yield, mild reaction conditions and less three wastes. However, the etherification reaction of the cyclohexyl alcohol compound still has the technical defect of low yield.
Therefore, there is an urgent need to develop a method for etherification of a cyclohexylalcohol compound with both high purity and high yield, in view of the above technical drawbacks.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for etherification of a cyclohexyl alcohol compound with both high purity and high yield. Compared with the prior art, the etherification reaction according to the invention not only has a purity of not less than 99%, but also has a yield of not less than 95%.
In order to realize the purpose of the invention, the following technical scheme is adopted: an etherification method of a cyclohexyl alcohol compound takes the cyclohexyl alcohol compound and halogenated hydrocarbon as raw materials to carry 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 type phase transfer catalyst and a cyclic crown ether phase transfer catalyst.
The etherification method according to the invention, wherein the quaternary ammonium salt phase transfer catalyst is selected from one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, and tetradecyltrimethylammonium chloride.
Preferably, the quaternary ammonium salt type phase transfer catalyst is selected from tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium bromide and benzyltriethylammonium chloride.
In one embodiment, the quaternary ammonium salt-based phase transfer catalyst is selected from tetrabutylammonium bromide.
The etherification process according to the present invention, wherein said cyclic crown ether phase transfer catalyst is selected from the group consisting of 18-crown-6, 15-crown-5, 12-crown-4 and alpha, beta, gamma-cyclodextrin.
Preferably, the cyclic crown ether phase transfer catalyst is selected from 18-crown-6, 15-crown-5, 12-crown-4.
In a specific embodiment, the cyclic crown ether phase transfer catalyst is selected from 18-crown-6.
The etherification method provided by the invention is characterized in that the general structure of the cyclohexyl alcohol compound is as follows:
Figure BDA0002751454910000041
wherein R is selected from carboxyl, ester group, cyclohexyl or substituted cyclohexyl, phenyl or substituted phenyl.
Preferably, R is selected from carboxy, phenyl or substituted phenyl.
In a particular embodiment, R is selected from carboxyl.
As a substituent on the cyclohexyl or phenyl group, the substituent is C1-C20Straight-chain alkyl or alkoxy of (A) and (C)1-C20Linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl.
Preferably, the substituent is C1-C10Straight-chain alkyl or alkoxy of (A) and (C)1-C10Linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl of (a);
more preferably, the substituent is C1-C6Straight-chain alkyl or alkoxy of (A) and (C)1-C6Linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl of (a);
and, most preferably, the substituent is C1-C4Straight-chain alkyl or alkoxy of (A) and (C)1-C4Linear alkyl or linear alkoxy substituted cyclohexyl or cyclopentyl.
In one embodiment, the substituent is C1-C4Linear alkyl group of (1).
On the other hand, the substitution position of R and the substituent on the cyclohexyl group or the phenyl group is advantageously a para position.
According to the etherification method, the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: (1.01-1.4).
Preferably, the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: (1.02-1.3); more preferably, the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: (1.03-1.2); and, most preferably, the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: (1.04-1.1).
In a specific embodiment, the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1: 1.05.
the etherification method according to the present invention, wherein the quaternary ammonium salt-based phase transfer catalyst is added in an amount of 1 to 10 mol% based on the number of moles of the cyclohexyl alcohol-based compound.
Preferably, the quaternary ammonium salt phase transfer catalyst is added in an amount of 2 to 8 mol% based on the moles of the cyclohexyl alcohol compound; more preferably, the quaternary ammonium salt-based phase transfer catalyst is added in an amount of 3 to 7 mol% based on the moles of the cyclohexyl alcohol-based compound; and, most preferably, the quaternary ammonium salt-based phase transfer catalyst is added in an amount of 4 to 6 mol% based on the number of moles of the cyclohexyl alcohol-based compound.
In a specific embodiment, the quaternary ammonium salt-based phase transfer catalyst is added in an amount of 5 mol% based on the moles of the cyclohexyl alcohol compound.
The etherification method according to the present invention, wherein the cyclic crown ether phase transfer catalyst is added in an amount of 0.4 to 2.4 mol% 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 mol% 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 mol% 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 mol% 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 mol% based on the moles of the cyclohexyl alcohol compound.
The etherification process according to the present invention, wherein the composite phase transfer catalyst further comprises potassium iodide.
The etherification method according to the present invention, wherein potassium iodide is added in an amount of 1 to 10 mol% based on the moles of the cyclohexyl alcohol compound.
Preferably, the amount of potassium iodide added is 2 to 8 mol% based on the number of moles of the cyclohexyl alcohol compound; more preferably, the amount of potassium iodide added is 3 to 7 mol% based on the number of moles of the cyclohexyl alcohol compound; and, most preferably, potassium iodide is added in an amount of 4 to 6 mol% based on the moles of the cyclohexyl alcohol compound.
In a specific embodiment, potassium iodide is added in an amount of 5 mol% based on the moles of the cyclohexyl alcohol compound.
The etherification method provided by the invention is characterized in that the temperature of the etherification reaction is 30-100 ℃.
Preferably, the temperature of the etherification reaction is 40-98 ℃; more preferably, the temperature of the etherification reaction is 50 to 95 ℃; and, most preferably, the temperature of the etherification reaction is 60 to 90 ℃.
In a specific embodiment, the temperature of the etherification reaction is 70 ℃.
Tetrahydrofuran and water are advantageously used as solvents for the etherification reaction.
The etherification method takes the cyclohexyl alcohol compound and the halogenated hydrocarbon as raw materials to carry out etherification reaction in the presence of a composite phase transfer catalyst. The composite phase transfer catalyst comprises a quaternary ammonium salt type phase transfer catalyst and a cyclic crown ether phase transfer catalyst. The inventors found that, in the etherification reaction, particularly when potassium iodide is further contained, the etherification reaction not only has a purity of not less than 99% but also has a yield of not less than 95%.
The materials, compounds, compositions and components of the present invention may be used in, or may be used in combination with, the methods and compositions of the present invention, or may be used in the practice of the methods and in the preparation of the compositions, or as products resulting from 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 collective combination and permutation of these compounds may not be explicitly made, each is specifically contemplated and described herein. For example, if an extraction aid component is disclosed and discussed, and a number of alternative solid state forms of that component are discussed, each and every combination and permutation of the possible reference aid components and solid state forms is 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 is 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 and should be considered disclosed.
In this specification and in 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 one and more than one (i.e., two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in this disclosure are approximate and thus may include values outside of the stated ranges. The numerical ranges may be stated 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 be further 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.
Reference in the specification and concluding claims to parts by weight of a particular element or component in a composition or article refers to the weight relationship between that element or component and any other elements or components in the composition or article, expressed as parts by weight.
Unless specifically indicated to the contrary, or implied by the context or customary practice in the art, all parts and percentages referred to herein are by weight and the weight percentages of a component are based on the total weight of the composition or product in which it is included.
References to "comprising," "including," "having," and similar terms in this specification 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. In order to avoid any doubt, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials unless stated to the contrary. In contrast, the term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination.
Furthermore, the contents of any referenced patent or non-patent document in this application are incorporated by reference in their entirety, especially with respect to definitions disclosed in the art (where not inconsistent with any definitions specifically provided herein) and general knowledge.
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 purely 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 in degrees Celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, 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
Figure BDA0002751454910000091
Adding 100ml of tetrahydrofuran into a three-necked bottle, adding 50g of water, adding 10g of 4-hydroxycyclohexanecarboxylic acid, adding 9.38g of bromopropane, adding 1g of tetrabutylammonium bromide, 0.5g of potassium iodide and 60.2 g of 18-crown ether, heating (80 ℃) to perform reflux reaction for 24 hours, after the reaction is finished, recovering a liquid-separating water layer for reuse, distilling an organic phase to recover tetrahydrofuran, adding 50ml of isopropanol, crystallizing, performing suction filtration to obtain 12.2g of a product, sampling, sending to a GC (gas chromatography) tester, wherein the purity is 99% and the yield is 95%.
Example 2
Figure BDA0002751454910000092
Adding 100ml of tetrahydrofuran into a three-necked bottle, adding 50g of water, adding 10g of raw material s-1, adding 6.8g of bromopropane, adding 1g of tetrabutylammonium bromide, 0.5g of potassium iodide and 60.2 g of 18-crown ether, heating (70 ℃) to perform reflux reaction for 24 hours, after the reaction is finished, recovering a liquid-separating water layer for reuse, distilling an organic phase to recover the tetrahydrofuran, adding 50ml of isopropanol, crystallizing, performing suction filtration to obtain 11.72g of a product, sampling, sending and measuring GC, wherein the purity is 99% and the yield is 96%.
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)

1.一种环己基醇类化合物的醚化方法，该方法以环己基醇类化合物和卤代烃作为原料，在复合相转移催化剂存在下进行醚化反应，其特征在于，所述复合相转移催化剂包含季铵盐类相转移催化剂和环状冠醚相转移催化剂。1. a method for etherification of cyclohexyl alcohol compounds, the method takes cyclohexyl alcohol compounds and halogenated hydrocarbons as raw materials, and carries out etherification reaction in the presence of a composite phase transfer catalyst, it is characterized in that, described composite phase transfer The catalyst includes a quaternary ammonium salt phase transfer catalyst and a cyclic crown ether phase transfer catalyst. 2.根据权利要求1所述的醚化方法，其中，所述季铵盐类相转移催化剂选自四丁基溴化铵、四丁基氯化铵、四丁基硫酸氢铵、苄基三乙基溴化铵、苄基三乙基氯化铵、三辛基甲基溴化铵、三辛基甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵、十四烷基三甲基溴化铵、十四烷基三甲基氯化铵的一种或多种。2. The method for etherification according to claim 1, wherein the quaternary ammonium salts phase transfer catalyst is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltrimonium Ethyl Ammonium Bromide, Benzyl Triethyl Ammonium Chloride, Trioctyl Methyl Ammonium Bromide, Trioctyl Methyl Ammonium Chloride, Dodecyl Trimethyl Ammonium Bromide, Dodecyl Trimethyl Ammonium One or more of tetradecyl ammonium chloride, tetradecyl trimethyl ammonium bromide and tetradecyl trimethyl ammonium chloride. 3.根据权利要求1所述的醚化方法，其中，所述环状冠醚相转移催化剂选自18-冠醚-6、15冠醚-5、12-冠醚-4和α、β、γ-环糊精。3. etherification method according to claim 1, wherein, described cyclic crown ether phase transfer catalyst is selected from 18-crown-6, 15-crown-5, 12-crown-4 and α, β, Gamma-cyclodextrin. 4.根据权利要求1所述的醚化方法，其中，所述环己基醇类化合物的通式结构如下：4. etherification method according to claim 1, wherein, the general structure of described cyclohexyl alcohol compound is as follows:
Figure FDA0002751454900000011
Figure FDA0002751454900000011
 其中，R选自羧基、酯基、环己基或取代的环己基、苯基或取代的苯基。wherein R is selected from carboxyl, ester, cyclohexyl or substituted cyclohexyl, phenyl or substituted phenyl. 5.根据权利要求1所述的醚化方法，其中，环己基醇类化合物与卤代烃的摩尔比为1：(1.01-1.4)。5. The method for etherification according to claim 1, wherein the molar ratio of the cyclohexyl alcohol compound to the halogenated hydrocarbon is 1:(1.01-1.4). 6.根据权利要求1所述的醚化方法，其中，基于环己基醇类化合物的摩尔数，所述季铵盐类相转移催化剂的加入量为1-10mol％。6 . The method for etherification according to claim 1 , wherein the quaternary ammonium salt-based phase transfer catalyst is added in an amount of 1-10 mol % based on the moles of the cyclohexyl alcohol-based compound. 7 . 7.根据权利要求1所述的醚化方法，其中，基于环己基醇类化合物的摩尔数，所述环状冠醚相转移催化剂的加入量为0.4-2.4mol％。7 . The etherification method according to claim 1 , wherein, based on the moles of cyclohexyl alcohol compounds, the addition amount of the cyclic crown ether phase transfer catalyst is 0.4-2.4 mol %. 8 . 8.根据权利要求1所述的醚化方法，其中，所述复合相转移催化剂进一步包含碘化钾。8. The etherification method of claim 1, wherein the composite phase transfer catalyst further comprises potassium iodide. 9.根据权利要求8所述的醚化方法，其中，基于环己基醇类化合物的摩尔数，碘化钾的加入量为1-10mol％。9 . The etherification method according to claim 8 , wherein, based on the mole number of the cyclohexyl alcohol compound, the addition amount of potassium iodide is 1-10 mol %. 10 . 10.根据权利要求1所述的醚化方法，其中，所述醚化反应的温度为30-100℃。10. The etherification method according to claim 1, wherein the temperature of the etherification reaction is 30-100°C.
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CN101434520A (en) * 2008-12-16 2009-05-20 淮海工学院 Preparation of tetrabromobisphenol A diallyl ether
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