CN117736074A - High-yield synthesis process of arylmethyl ether - Google Patents
High-yield synthesis process of arylmethyl ether Download PDFInfo
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- CN117736074A CN117736074A CN202311563339.8A CN202311563339A CN117736074A CN 117736074 A CN117736074 A CN 117736074A CN 202311563339 A CN202311563339 A CN 202311563339A CN 117736074 A CN117736074 A CN 117736074A
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- iodide
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- 238000000034 method Methods 0.000 title claims abstract description 26
- -1 arylmethyl ether Chemical compound 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 28
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000002989 phenols Chemical class 0.000 claims abstract description 17
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 12
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000007069 methylation reaction Methods 0.000 claims abstract description 11
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000011987 methylation Effects 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims abstract description 9
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims abstract description 8
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims abstract description 5
- ZLHWTGZMAWUUMD-UHFFFAOYSA-M ethyl(tripropyl)azanium;iodide Chemical compound [I-].CCC[N+](CC)(CCC)CCC ZLHWTGZMAWUUMD-UHFFFAOYSA-M 0.000 claims abstract description 4
- PPJJASFMQNPUER-UHFFFAOYSA-N tetradecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCC[NH3+] PPJJASFMQNPUER-UHFFFAOYSA-N 0.000 claims abstract description 4
- VRKHAMWCGMJAMI-UHFFFAOYSA-M tetrahexylazanium;iodide Chemical compound [I-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC VRKHAMWCGMJAMI-UHFFFAOYSA-M 0.000 claims abstract description 4
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims abstract description 4
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000013094 purity test Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 125000005002 aryl methyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000012022 methylating agents Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a high-yield synthesis process of anisole, which comprises the following steps: taking a phenolic compound as a raw material, taking dimethyl carbonate as a methylation reagent, adding a quaternary ammonium salt catalyst and a nitrogenous organic base, uniformly mixing, then, entering a reactor, carrying out a reaction under 140-180 ℃ self-pressure for less than 3 hours, then, decompressing, and detecting the purity of an arylmethyl ether product in the decompressed material; the quaternary ammonium salt catalyst is selected from one or more of tetraethylammonium iodide, ethyl tripropyl ammonium iodide, tetrapropyl ammonium iodide, tetrabutylammonium iodide, tetrahexyl ammonium iodide, tetradecyl ammonium iodide, tetraethylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bromide; the nitrogenous organic base is selected from one or more of 1, 3-dimethyl-2-imidazolone and 1, 3-dimethyl-tetrahydro-2-pyrimidinone. The yield of the product of the invention is more than 90%, and the yield of the optimized product can reach up to 99%.
Description
Technical Field
The invention relates to the technical field of green chemical synthesis of compounds, in particular to a high-yield synthesis process of anisole.
Background
In the traditional method, phenol or phenol containing functional groups is generally used as a raw material, and dimethyl sulfate is used as a methylation reagent to react to obtain anisole products. But dimethyl sulfate (DMS) is a highly toxic substance, and generates a large amount of highly toxic waste water and solid waste, which has serious environmental pollution. Dimethyl carbonate (DMC) has been widely used as a methylating agent nowadays because of its low toxicity and low environmental impact. The methylation process of DMC is adopted, no waste water is generated in the production process, and sodium hydroxide is not used as an acid binding agent in the production process. Saving the production cost, avoiding the use of chloroform, DMS and sodium hydroxide, and belonging to the environment-friendly low-carbon production process.
In the prior art, for example, CN1066317714A discloses a method for synthesizing 2, 6-dimethoxy phenol, pyrogallic acid and dimethyl carbonate are reacted in a micro-reactor, tetrabutylammonium bromide is used as a reaction catalyst, methanol is used as a solvent, the reaction condition is 110-170 ℃, the reaction pressure is 5MPa, the product yield is 69-92%, the relation between the reaction temperature and the product yield is recorded in 0006 section, and the increase of the reaction temperature has no positive effect on the improvement of the yield and the purity of the reaction product. It can be seen that even if continuous production of the microreactor is realized, the reaction conditions are still more severe, higher reaction pressure is required, the energy consumption is larger, and the product yield is not ideal.
Disclosure of Invention
In order to solve the technical problems of high energy consumption and unsatisfactory yield in the existing process for synthesizing the aryl methyl ether, the high-yield synthetic process for the aryl methyl ether is provided. The invention adopts intermittent synthesis process to prepare related anisole products, no toxic and harmful substances are generated in the whole reaction process, the method is a chemical synthesis process, the product yield is more than 90wt%, and the optimized product yield can reach up to 99wt%.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the high-yield synthesis process of the aryl methyl ether comprises the following steps:
taking a phenolic compound as a raw material, taking dimethyl carbonate (DMC) as a methylation reagent, adding a quaternary ammonium salt catalyst, adding or not adding a nitrogenous organic base, uniformly mixing, then entering a reactor, reacting at 140-180 ℃ under self-pressure for less than 3 hours, cooling and decompressing, and detecting the purity of an arylmethyl ether product in the decompressed material;
the quaternary ammonium salt catalyst has the following general formula:
wherein R is 1 -R 4 Each independently is a C2-C7 linear or branched alkane wherein X is one of F, cl, br, I;
the nitrogenous organic base is selected from one or more of 1, 3-dimethyl-2-imidazolone and 1, 3-dimethyl-tetrahydro-2-pyrimidinone.
Further, the quaternary ammonium salt catalyst is selected from one or more of tetraethylammonium iodide, ethyltripropylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrahexylammonium iodide, tetradecylammonium iodide, tetraethylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bromide.
Further, when X in the selected quaternary ammonium salt catalyst is I, the nitrogenous organic base is not added, the selected reaction temperature is 150-170 ℃, and the reaction time is more than 0.5h and not more than 2h; when X in the selected quaternary ammonium salt catalyst is Cl or Br, adding the nitrogenous organic base, wherein the selected reaction temperature is 160-180 ℃ and the reaction time is 1-2 h.
Further, the phenolic compound is selected from one of phenol, o-methylphenol, m-methylphenol, p-methylphenol, catechol, resorcinol, hydroquinone, 1-naphthol and 2-naphthol.
Further, the molar ratio of the phenolic compound to the dimethyl carbonate to the quaternary ammonium salt catalyst is 1:5-10:0.1; the molar amount of the nitrogen-containing organic base is 3 to 5 times, preferably 3.5 to 4.5 times the molar amount of the phenolic compound.
The decompressed material is a mixture containing the anisole product, and technicians can separate the decompressed material to obtain the purified anisole product, for example, rectification separation and purification can be adopted, and the general process is as follows: and (3) rectifying the decompressed material for the first time: dimethyl carbonate and an alcohol byproduct are obtained at the top of the rectifying tower, and the alcohol byproduct and the dimethyl carbonate can be further rectified and separated for recycling; and (3) carrying out secondary rectification separation on the materials in the tower kettle to obtain an anisole product, a quaternary ammonium salt catalyst or a mixture of the anisole product and the nitrogenous organic base, wherein the quaternary ammonium salt catalyst or the mixture of the quaternary ammonium salt catalyst and the nitrogenous organic base can be recycled. The solvent, the catalyst and the like can be recycled, so that the batch production of the anisole can be realized. The rectification conditions used by different anisole are different, and the materials obtained after the relevant synthesis pressure relief are subjected to the rectification scheme test and the further rectification scheme confirmation according to the boiling point of each material and the computer simulation of rectification.
The beneficial technical effects are as follows:
in order to obtain the anisole, the invention takes phenolic compounds as raw materials, takes dimethyl carbonate as a methylating agent, and adds an iodine-containing quaternary ammonium salt catalyst during synthesis, so that the anisole can be obtained in high yield by self-pressure reaction at a lower temperature (less than or equal to 180 ℃); or a chlorine-containing or bromine-containing quaternary ammonium salt catalyst is adopted during synthesis, and simultaneously a nitrogen-containing organic base (DMI and/or DMPU) is added to play a role in synergistic catalysis, so that the reaction conversion rate and the reaction rate are obviously increased, and the reaction is completed in a short time and high efficiency under the condition of self pressure (the reaction pressure is less than 1.5MPa in the reaction process).
Drawings
FIG. 1 is a graph showing the pressure and the reaction time of the self-pressure reaction in the system under the reaction conditions of test example 4, test example 6 and test example 34.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Hereinafter tetraethylammonium iodide is abbreviated as TEAI, ethyltripropylammonium iodide is abbreviated as EPAI, tetrapropylammonium iodide is abbreviated as TPAI, tetrabutylammonium iodide is abbreviated as TBAI, tetrahexylammonium iodide is abbreviated as THAI, tetradecylammonium iodide is abbreviated as TDAI, tetraethylammonium bromide is abbreviated as TEAB, tetrabutylammonium chloride is abbreviated as TBAC, and tetrabutylammonium bromide is abbreviated as TBAB.
The purity of the product in the following table corresponds to the yield of the product.
Example 1
The product of the embodiment is anisole, and the specific synthetic process is as follows:
taking 0.01mol of phenol as a raw material, 0.05mol of dimethyl carbonate as a methylation reagent, respectively adding 0.001mol of quaternary ammonium salt as shown in the following table 1 as a catalyst, examining the influence of adding or not adding DMI on the reaction, and if adding the DMI, adding according to the adding amount of 5g of the DMI;
the reaction materials are uniformly mixed and then enter a reactor to react for 0.5h under the self-pressure at 160 ℃, then the reaction materials are cooled and decompressed, the decompressed materials are sampled and then are directly subjected to product purity test, and the test process is as follows: the composition of the resulting material was analyzed by liquid chromatography. The chromatographic conditions are as follows: the mobile phase is a mixed solution of methanol and water (volume ratio of methanol to water is 70:30), the detection wavelength of the UV detector is 254nm, the analysis column is XDB-C18, and the flow rate is set to be 1mL/min. The analysis process comprises the following steps: and taking 0.1mL of a sample to be tested, diluting the sample to 2mL by using a mobile phase, and injecting the sample into a liquid chromatograph for testing and analysis.
Specific reaction conditions and product purity are shown in table 1 below.
TABLE 1 anisole purity synthesized with or without DMI and different quaternary ammonium salt catalysts
(Note: x indicates that DMI was not added, and v indicates that DMI was added)
As is clear from Table 1, the activity of the bromide or chloride quaternary ammonium salt catalyst such as other quaternary ammonium salt iodide and other quaternary ammonium salt catalyst such as TBAC, TBAB, TEAB on the methylation reaction of phenol is not high, and after the DMI is added, the catalyst can form a homogeneous catalytic system with TBAC, TBAB, TEAB respectively, so that anisole products can be efficiently catalyzed and synthesized. The catalytic activity of the bromide or chloride quaternary ammonium salt catalyst can be improved to a large extent by adding the DMI.
Example two
Taking 0.01mol of phenol as a raw material, taking 0.05mol of dimethyl carbonate as a methylation reagent, respectively adding one of 0.001mol of TBAB and TEAB, TBAC, TBAI, and respectively examining the influence of adding DMI or DMPU under the same catalyst on the reaction (all added according to the addition amount of 5 g); the above-mentioned reaction materials are uniformly mixed, then fed into a reactor and reacted for 0.5h-2h under self-pressure at 160-180 deg.C, and all the tests are shown in the following Table 2, then cooled and decompressed, and the decompressed materials are sampled, then directly subjected to product purity test, and the test process is identical to that of example one.
The anisole product purity is shown in table 2 below.
TABLE 2 same class of quaternary ammonium salt catalysts, anisole purity under the action of different nitrogen-containing organic bases
From Table 2, it is clear that DMI or DMPU can form a homogeneous system with different quaternary ammonium salt catalysts respectively, and efficiently catalyze the synthesis of anisole.
Example III
Taking 0.01mol of phenol as a raw material, 0.05mol of dimethyl carbonate as a methylation reagent, adding 0.001mol of TBAI, and respectively observing the influence of adding or not adding the DMI at different reaction temperatures (adding according to the adding amount of 5 g); the reaction materials are uniformly mixed and then enter a reactor to react for 2 hours under the self-pressure at 120-170 ℃, then the reaction materials are cooled and decompressed, the decompressed materials are sampled and then are directly subjected to product purity test, the test process is the same as that of the first embodiment, and the anisole product purity is shown in the table 3 below.
TABLE 3TBAI catalyst, arylmethylether purity with and without DMI added at various reaction temperatures
(Note: x indicates that DMI was not added, and v indicates that DMI was added)
As shown in Table 3, the iodide catalyst of the quaternary ammonium salt has higher catalytic activity, and the catalytic performance of the iodide catalyst of the quaternary ammonium salt is improved to a certain extent by adding DMI into a synthesis system. When the iodine compound TBAI of the quaternary ammonium salt is used as a catalyst, the product purity of more than 98 percent can be achieved after the reaction for 2 hours at 150-170 ℃ without adding DMI.
Example IV
Taking 0.01mol of phenolic compound as a raw material, taking 0.05-0.1 mol of dimethyl carbonate as a methylation reagent, and under the action of a 0.001mol TBAI catalyst without adding DMI; the raw materials are mixed uniformly and then enter a reactor to react for 1h under self-pressure at 170 ℃, then the reaction is cooled and decompressed, the decompressed materials are sampled and then directly subjected to product purity test, the test process is the same as that of the first embodiment, and the product purity of the arylmethyl ether is shown in the following table 4.
TABLE 4 purity of the products of different phenolic Compounds starting materials with TBAI catalyst without DMI addition
As is clear from Table 4, TBAI has little difference in catalytic efficiency for various phenolic compounds, and the yield of the total substituted products corresponding to other phenolic compounds, except catechol and resorcinol, is as high as 92wt% or more.
Example five
Taking 0.01mol of phenolic compound as a raw material, taking 0.05-0.1 mol of dimethyl carbonate as a methylation reagent, adding DMPU, and respectively adding 0.001mol of TBAB catalyst; after the raw materials are uniformly mixed, the reaction is carried out for 1h to 2h under the self-pressure at 170 ℃, then the pressure is released by cooling, the materials after the pressure release are sampled and then the purity of the product is directly tested, the testing process is the same as that of the first embodiment, and the purity of the product of the arylmethyl ether is shown in the table 5 below.
TABLE 5 purity of the products of different phenolic starting materials with DMPU and TBAB catalysts
As shown in Table 5, TBAB has high catalytic efficiency on different phenolic compounds by reacting for 1h at 170 ℃ in the presence of DMPU, and the yield of the fully substituted products corresponding to the different phenolic compounds is as high as more than 90 wt%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The high-yield synthesis process of the anisole is characterized by comprising the following steps of:
taking a phenolic compound as a raw material, taking dimethyl carbonate as a methylation reagent, adding a quaternary ammonium salt catalyst, adding or not adding a nitrogenous organic base, uniformly mixing, then, entering a reactor, reacting at 140-180 ℃ under self-pressure for less than 3 hours, cooling and decompressing, and detecting the purity of an arylmethyl ether product in the decompressed material;
the quaternary ammonium salt catalyst has the following general formula:
wherein R is 1 -R 4 Each independently is a C2-C7 linear or branched alkane wherein X is one of F, cl, br, I;
the nitrogenous organic base is selected from one or more of 1, 3-dimethyl-2-imidazolone and 1, 3-dimethyl-tetrahydro-2-pyrimidinone.
2. The process for synthesizing anisole in high yield according to claim 1, wherein the quaternary ammonium salt catalyst is one or more selected from tetraethylammonium iodide, ethyltripropylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrahexylammonium iodide, tetradecylammonium iodide, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.
3. The process for synthesizing anisole in high yield according to claim 2, wherein when X is I in the selected quaternary ammonium salt catalyst, the nitrogen-containing organic base is not added, the selected reaction temperature is 150 ℃ to 170 ℃, and the reaction time is more than 0.5h and not more than 2h; when X in the selected quaternary ammonium salt catalyst is Cl or Br, adding the nitrogenous organic base, wherein the selected reaction temperature is 160-180 ℃ and the reaction time is 1-2 h.
4. The process for synthesizing anisole in high yield according to claim 1, wherein said phenolic compound is one selected from the group consisting of phenol, o-methylphenol, m-methylphenol, p-methylphenol, catechol, resorcinol, hydroquinone, 1-naphthol, 2-naphthol.
5. The process for synthesizing anisole in high yield according to claim 1, wherein the molar ratio of the phenolic compound, the dimethyl carbonate and the quaternary ammonium salt catalyst is 1:5-10:0.1, and the molar amount of the nitrogen-containing organic base is 3-5 times the molar amount of the phenolic compound.
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