CN1271027C - Method of synthesizing dihalogenated aromatic ether by phase transfer - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000008378 aryl ethers Chemical class 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 11
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical group CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 5
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims 5
- 239000002253 acid Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 10
- 238000004817 gas chromatography Methods 0.000 abstract description 8
- 238000003408 phase transfer catalysis Methods 0.000 abstract description 7
- 150000002989 phenols Chemical class 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000007036 catalytic synthesis reaction Methods 0.000 description 6
- -1 2,4-dichlorophenylisopropyl ether Chemical compound 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- FAXWFCTVSHEODL-UHFFFAOYSA-N 2,4-dibromophenol Chemical compound OC1=CC=C(Br)C=C1Br FAXWFCTVSHEODL-UHFFFAOYSA-N 0.000 description 4
- OFAPWTOOMSVMIU-UHFFFAOYSA-N 2,4-dichloro-5-nitrophenol Chemical compound OC1=CC([N+]([O-])=O)=C(Cl)C=C1Cl OFAPWTOOMSVMIU-UHFFFAOYSA-N 0.000 description 4
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 2
- YSTVONWNUGLKSC-UHFFFAOYSA-N 2,4-dichloro-1-propoxybenzene Chemical compound CCCOC1=CC=C(Cl)C=C1Cl YSTVONWNUGLKSC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 2
- QZYDOKBVZJLQCK-UHFFFAOYSA-N 1,2-diethoxybenzene Chemical compound CCOC1=CC=CC=C1OCC QZYDOKBVZJLQCK-UHFFFAOYSA-N 0.000 description 1
- VWGNFIQXBYRDCH-UHFFFAOYSA-N 1,4-diethoxybenzene Chemical compound CCOC1=CC=C(OCC)C=C1 VWGNFIQXBYRDCH-UHFFFAOYSA-N 0.000 description 1
- SKZUJEUNTYZIRO-UHFFFAOYSA-N 2,4-dichloro-1-propan-2-yloxybenzene Chemical compound CC(C)OC1=CC=C(Cl)C=C1Cl SKZUJEUNTYZIRO-UHFFFAOYSA-N 0.000 description 1
- XZPYWSMHAVVJNK-UHFFFAOYSA-N ClC=1C=C(C=C(C=1Cl)O)[N+](=O)[O-] Chemical compound ClC=1C=C(C=C(C=1Cl)O)[N+](=O)[O-] XZPYWSMHAVVJNK-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- ZCMJDJGHNYAWSZ-UHFFFAOYSA-N [1-chloro-2-(1-chloro-2-phenylpropan-2-yl)oxypropan-2-yl]benzene Chemical compound C1(=CC=CC=C1)C(C)(CCl)OC(C)(C1=CC=CC=C1)CCl ZCMJDJGHNYAWSZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种相转移催化合成二卤代芳香醚的方法，以二卤代酚为原料，在NaOH水溶液中，加入相转移催化剂，滴加溴代烃进行反应，生成二卤代芳香醚，再分离提纯而得成品，反应中只加入水作为溶剂，不加任何其它有机溶剂。由于反应中不使用有机溶剂，因此在工艺上减少了有机溶剂回收和精馏等步骤，对环境友好，易于工业化生产。而且，二卤代酚、NaOH水溶液及相转移催化剂的混合物中由于不含有机溶剂，能加热到比较高的温度(90℃以上)，大大加快了与溴代烃的反应速度，并使得率提高。用本发明的方法制取二卤代芳醚，得率可达到90%以上，气相色谱分析纯度可达到95%以上。A method for synthesizing dihalogenated aromatic ethers by phase transfer catalysis, using dihalogenated phenols as raw materials, adding a phase transfer catalyst in NaOH aqueous solution, adding brominated hydrocarbons dropwise for reaction to generate dihalogenated aromatic ethers, and then separating and purifying To obtain the finished product, only water is added as a solvent in the reaction without adding any other organic solvents. Since no organic solvent is used in the reaction, steps such as organic solvent recovery and rectification are reduced in the process, which is environmentally friendly and easy for industrial production. Moreover, since the mixture of dihalophenol, NaOH aqueous solution and phase transfer catalyst does not contain organic solvents, it can be heated to a relatively high temperature (above 90°C), which greatly accelerates the reaction speed with brominated hydrocarbons and improves the efficiency. . The method of the present invention is used to prepare dihalogenated aryl ethers, and the yield can reach more than 90%, and the purity can reach more than 95% by gas chromatography.
Description
技术领域technical field
本发明涉及一种制备二卤代芳香醚的方法，一种相转移催化合成二卤代芳香醚的方法。The invention relates to a method for preparing dihalogenated aromatic ethers, and a method for synthesizing dihalogenated aromatic ethers by phase transfer catalysis.
背景技术Background technique
2，4-二氯苯异丙基醚和硝基2，4-二氯异丙基醚等二卤代芳香醚是一类重要的有机中间体。制备这类二卤代芳香醚可使用相转移催化合成法，由二卤代酚与卤代烃反应制得。传统的相转移催化合成法需使用有机溶剂，例如，《广州化学》第26卷第4期28-30页“1，4-二乙氧基苯的相转移催化合成”一文介绍的二乙氧基苯的相转移催化合成中采用甲苯作溶剂。这种方法需对有机溶剂进行回收和精馏，工艺较复杂。同时在对芳醚再进行取代等反应时，由于脱溶剂不彻底而带来副产物，需进行再分离。使后续工艺复杂化。Dihalogenated aromatic ethers such as 2,4-dichlorophenylisopropyl ether and nitro 2,4-dichloroisopropyl ether are important organic intermediates. The preparation of such dihalogenated aromatic ethers can be prepared by the reaction of dihalogenated phenols and halogenated hydrocarbons by phase transfer catalytic synthesis. The traditional phase-transfer catalytic synthesis method requires the use of organic solvents, for example, the diethoxybenzene introduced in the article "Phase-transfer catalytic synthesis of 1,4-diethoxybenzene" in Volume 26, Issue 4, Page 28-30 of "Guangzhou Chemistry". Toluene was used as solvent in the phase transfer catalytic synthesis of phenylbenzene. This method needs to recover and rectify the organic solvent, and the process is more complicated. At the same time, when the aryl ether is replaced and other reactions are carried out, by-products are brought due to incomplete desolventization, which needs to be separated again. complicate subsequent processes.
发明内容Contents of the invention
本发明旨在提出一种不需有机溶剂的制备二卤代芳香醚的方法，一种相转移催化合成二卤代芳香醚的方法。The present invention aims to propose a method for preparing dihalogenated aromatic ethers without an organic solvent, and a method for synthesizing dihalogenated aromatic ethers by phase transfer catalysis.
这种相转移催化合成二卤代芳香醚的方法以二卤代酚为原料，在NaOH水溶液中，加入相转移催化剂，滴加溴代烃进行反应，生成二卤代芳香醚，再分离提纯而得成品，反应中只加入水作为溶剂，不加任何其它有机溶剂。This phase transfer catalyzed method for synthesizing dihalogenated aromatic ethers uses dihalogenated phenols as raw materials. In NaOH aqueous solution, a phase transfer catalyst is added, and brominated hydrocarbons are added dropwise to react to generate dihalogenated aromatic ethers, which are then separated and purified. To obtain the finished product, only water is added as a solvent in the reaction without adding any other organic solvents.
本发明的相转移催化合成二卤代芳香醚的方法，由于反应中不使用有机溶剂，因此在工艺上减少了有机溶剂回收和精馏等步骤，对环境友好，易于工业化生产。而且，二卤代酚、NaOH水溶液及相转移催化剂的混合物，由于不含有机溶剂，能加热到比较高的温度(90℃以上)，大大加快了与溴代烃的反应速度，并使得率提高，纯度可达到95％以上。The method for synthesizing dihalogenated aromatic ethers by phase-transfer catalysis of the present invention does not use organic solvents in the reaction, so steps such as organic solvent recovery and rectification are reduced in the process, which is environmentally friendly and easy for industrial production. Moreover, the mixture of dihalophenol, NaOH aqueous solution and phase transfer catalyst, because it does not contain organic solvents, can be heated to a relatively high temperature (above 90°C), which greatly speeds up the reaction speed with brominated hydrocarbons and improves the efficiency. , the purity can reach more than 95%.
具体实施方式Detailed ways
这种相转移催化合成二卤代芳香醚的方法以二卤代酚为原料，在NaOH水溶液中，加入相转移催化剂，滴加溴代烃进行反应，生成二卤代芳香醚，再分离提纯而得成品，反应中只加入水作为溶剂，不加任何其它有机溶剂。这种醚化方法是亲核取代，有机相为溴代烃，无机相为碱的取代苯酚盐，取代苯酚在碱的作用下生成的负离子作为一个亲核试剂，被相转移催化剂携带入有机相中与卤代烃进行亲核取代反应。反应后生成的无机盐又通过相转移催化剂带到水相，有机相经碱水洗涤后溶于醚中的取代苯酚可重新回到水相。最后得到纯度高的芳香醚产品。This phase transfer catalyzed method for synthesizing dihalogenated aromatic ethers uses dihalogenated phenols as raw materials. In NaOH aqueous solution, a phase transfer catalyst is added, and brominated hydrocarbons are added dropwise to react to generate dihalogenated aromatic ethers, which are then separated and purified. To obtain the finished product, only water is added as a solvent in the reaction without adding any other organic solvents. This etherification method is nucleophilic substitution, the organic phase is a brominated hydrocarbon, and the inorganic phase is a substituted phenate of a base. The anion generated by the substituted phenol under the action of a base acts as a nucleophile and is carried into the organic phase by a phase transfer catalyst. nucleophilic substitution reaction with halogenated hydrocarbons. The inorganic salt generated after the reaction is brought to the water phase through the phase transfer catalyst, and the substituted phenol dissolved in ether can return to the water phase after the organic phase is washed with alkaline water. Finally, an aromatic ether product with high purity is obtained.
其反应式如下：Its reaction formula is as follows:
式中，R＝CnH2n+1，如异丙基、正丙基、正丁基、乙基等。X＝Br，Y＝NO2、SO3H。In the formula, R=C n H 2n+1 , such as isopropyl, n-propyl, n-butyl, ethyl, etc. X=Br, Y= NO2 , SO3H .
相转移催化剂为季铵盐类或鏻盐类，具有以下结构：Phase transfer catalysts are quaternary ammonium salts or phosphonium salts with the following structure:
式中R1、R2、R3、R4分别为CnH2n+1(n＝1-16)的脂肪族烃基或芳基，烃基可以是相同也可不同。季铵盐类如：三乙基苄基氯化铵，十六烷基三甲基溴化铵。鏻盐类如：四丁基氯化鏻。In the formula, R 1 , R 2 , R 3 , and R 4 are aliphatic hydrocarbon groups or aryl groups of C n H 2n+1 (n=1-16), respectively, and the hydrocarbon groups may be the same or different. Quaternary ammonium salts such as: triethylbenzyl ammonium chloride, cetyltrimethylammonium bromide. Phosphonium salts such as: tetrabutylphosphonium chloride.
本发明的方法中，NaOH可以分二步加入，其过程为：在反应器中加入二卤代酚、部分固体NaOH、相转移催化剂和水，加热升温并搅拌，当温度达到90-120℃时，缓缓滴加溴代烃RBr，滴加过程中控制温度为90-100℃，搅拌4-6h后，再加入其余NaOH，再反应1-2h，反应结束后冷却至50℃以下，用NaOH水溶液洗涤除去杂质，分液后取出下层有机层。In the method of the present invention, NaOH can be added in two steps, and the process is: add dihalophenol, part of solid NaOH, phase transfer catalyst and water into the reactor, heat up and stir, when the temperature reaches 90-120°C , slowly add brominated hydrocarbon RBr dropwise, control the temperature at 90-100°C during the dropping process, stir for 4-6h, then add the rest of NaOH, and then react for 1-2h, cool to below 50°C after the reaction, and use NaOH Impurities were removed by washing with aqueous solution, and the lower organic layer was taken out after liquid separation.
NaOH分二步加入可使前段反应时，混合物的碱性不会过高，可防止二卤代酚发生水解而降低反应效果，并可使得率提高，达到90％以上。Adding NaOH in two steps can make the alkalinity of the mixture not too high during the first stage of the reaction, prevent the dihalophenol from being hydrolyzed and reduce the reaction effect, and increase the yield to more than 90%.
本发明的相转移催化合成二卤代芳香醚的方法中，各原料加入的量以mol计为二卤代酚∶溴代烃∶NaOH＝1∶1-3∶1-4，水与NaOH重量比为3-7∶1，季铵盐类或鏻盐类相转移催化剂与二氯苯酚的重量比为0.002-0.01∶1。In the method for phase-transfer catalytic synthesis of dihalogenated aromatic ethers of the present invention, the amount of each raw material added is calculated in mol as dihalophenol: brominated hydrocarbon: NaOH=1: 1-3: 1-4, water and NaOH weight The ratio is 3-7:1, and the weight ratio of the quaternary ammonium salt or phosphonium salt phase transfer catalyst to dichlorophenol is 0.002-0.01:1.
本发明的相转移催化合成二卤代芳香醚的方法中的二卤代酚采用二氯苯酚、溴代烃采用溴代异丙烷时，所制得的二卤代芳香醚为2，4-二氯苯异丙基醚。In the method for synthesizing dihalogenated aromatic ethers by phase transfer catalysis of the present invention, when dihalophenols are dichlorophenols and brominated hydrocarbons are bromoisopropane, the prepared dihalogenated aromatic ethers are 2,4-dihalogenated aromatic ethers. Chlorophenylisopropyl ether.
本发明的相转移催化合成二卤代芳香醚的方法中的二卤代酚采用二氯-5-硝基苯酚、溴代烃为溴代正丙烷时，所制得的二卤代芳香醚为5-硝基2，4-二氯苯正丙基醚。When the dihalophenol in the method for the phase transfer catalysis synthesis of dihalogenated aromatic ethers of the present invention adopts dichloro-5-nitrophenol and brominated hydrocarbon is brominated n-propane, the prepared dihalogenated aromatic ethers are 5-Nitro 2,4-dichlorophenyl-n-propyl ether.
实施例1：Example 1:
取2，4-二氯代苯酚16.3g，NaOH 6g，十六烷基三甲基溴化铵0.06g，加入反应器中，加25ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使2，4-二氯代苯酚溶解，温度升至105℃时，开始通过滴液漏斗滴加21.96g溴代异丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应5h，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品异丙基2，4-二氯代苯醚18.36g，产品经气相色谱分析纯度96％，得率86％。本例中氢氧化钠一次加入。Take 16.3g of 2,4-dichlorophenol, 6g of NaOH, and 0.06g of cetyltrimethylammonium bromide, add them to the reactor, and add 25ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 2,4-dichlorophenol, and when the temperature rises to 105°C, start to add 21.96 g of bromophenol dropwise through the dropping funnel. Isopropane, after 1h, the dropwise addition is completed, the reaction temperature is about 95°C, reflux for 5h, and the material is discharged after cooling. After washing with 2% NaOH aqueous solution, the product isopropyl 2,4-dichlorophenyl ether 18.36 g, the purity of the product analyzed by gas chromatography is 96%, and the yield is 86%. In this example, sodium hydroxide was added at one time.
实施例2：Example 2:
取2，4-二氯代苯酚16.5g，NaOH 5g，十六烷基三甲基溴化铵0.06g，加入反应器中，加25ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使2，4-二氯代苯酚溶解，温度升至105℃时，开始通过滴液漏斗滴加21.96g溴代异丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应3h，然后补加1gNaOH，再回流2h，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品异丙基2，4-二氯代苯醚19.1g，产品经气相色谱分析纯度98％，得率91.5％。Take 16.5g of 2,4-dichlorophenol, 5g of NaOH, and 0.06g of cetyltrimethylammonium bromide, add them to the reactor, and add 25ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 2,4-dichlorophenol, and when the temperature rises to 105°C, start to add 21.96 g of bromophenol dropwise through the dropping funnel. Isopropane, after 1h, the dropwise addition is completed, the reaction temperature is about 95°C, reflux for 3h, then add 1g of NaOH, and then reflux for 2h, cool and discharge, wash with 2% NaOH aqueous solution and separate to obtain the product isopropyl 2 , 19.1 g of 4-dichlorophenyl ether, the product was analyzed by gas chromatography with a purity of 98%, and a yield of 91.5%.
实施例3：Example 3:
取5-硝基-2，4-二氯代苯酚20.9g，NaOH 6g，三乙基苄基氯化铵0.05g，加入反应器中，加40ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使5-硝基-2，4-二氯代苯酚溶解，温度升至95℃时，开始通过滴液漏斗滴加19.5g溴代异丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应3h，然后补加1g NaOH，再回流2小时，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品5-硝基-2，4-二氯代苯异丙基醚24g，经产品物理常数分析，熔点40-41.2℃，气相色谱分析纯度96％，得率91.8％。Get 20.9g of 5-nitro-2,4-dichlorophenol, 6g of NaOH, 0.05g of triethylbenzyl ammonium chloride, add in the reactor, add 40ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 5-nitro-2,4-dichlorophenol, and when the temperature rises to 95°C, start to drop through the dropping funnel Add 19.5g of bromoisopropane, drop it after 1h, the reaction temperature is about 95°C, reflux for 3h, then add 1g of NaOH, and then reflux for 2 hours, discharge after cooling, wash with 2% NaOH aqueous solution and divide 24 g of the product 5-nitro-2,4-dichlorophenylisopropyl ether was obtained from the liquid. According to the analysis of product physical constants, the melting point was 40-41.2° C., the purity by gas chromatography was 96%, and the yield was 91.8%.
实施例4：Example 4:
取5-硝基-2，4-二氯代苯酚20.9g，NaOH 6g，三乙基苄基氯化铵0.1g，加入反应器中，加35ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使5-硝基-2，4-二氯代苯酚溶解，温度升至95℃时，开始通过滴液漏斗滴加36.3g溴代正丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应3h，然后补加1g NaOH，再回流2小时，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品5-硝基-2，4-二氯代苯丙基醚23.76g，产品经气相色谱分析纯度98％，得率92.8％。Take 20.9 g of 5-nitro-2,4-dichlorophenol, 6 g of NaOH, and 0.1 g of triethylbenzyl ammonium chloride, add them to the reactor, and add 35 ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 5-nitro-2,4-dichlorophenol, and when the temperature rises to 95°C, start to drop through the dropping funnel Add 36.3g of bromo-n-propane, dropwise after 1h, the reaction temperature is about 95°C, reflux for 3h, then add 1g of NaOH, and then reflux for 2 hours, discharge after cooling, wash with 2% NaOH aqueous solution and divide 23.76 g of the product 5-nitro-2,4-dichlorophenylpropyl ether was obtained from the liquid, and the product was analyzed by gas chromatography with a purity of 98% and a yield of 92.8%.
实施例5：Example 5:
取2，4-二溴代苯酚25.1g，NaOH 10g，四丁基氯化鏻0.06g，加入反应器中，加56ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使2，4-二溴代苯酚溶解，温度升至105℃时，开始通过滴液漏斗滴加24.4g溴代异丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应3h，然后补加4g NaOH，再回流2h，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品2，4-二溴代苯异丙基醚28.1g，经产品经气相色谱分析纯度96％，得率92.3％。Get 25.1g of 2,4-dibromophenol, 10g of NaOH, 0.06g of tetrabutylphosphonium chloride, add in the reactor, add 56ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 2,4-dibromophenol, and when the temperature rises to 105°C, start to add 24.4 g of bromophenol dropwise through the dropping funnel. Isopropane, dropwise is completed after 1h, the reaction temperature is about 95°C, reflux for 3h, then add 4g NaOH, and then reflux for 2h, cool and discharge, wash with 2% NaOH aqueous solution and separate to obtain product 2, 4 - 28.1 g of dibromophenylisopropyl ether, the purity of the product is 96% through gas chromatography analysis, and the yield is 92.3%.
实施例6：Embodiment 6:
取2，4-二氯代苯酚16.5g，NaOH 10g，三乙基苄基氯化铵0.16g加入反应器中，加36ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使2，4-二氯代苯酚溶解，温度升至105℃时，开始通过滴液漏斗滴加26.8g溴代正丙烷，1h后滴加完毕，反应温度在95℃左右，回流反应3h，然后补加2gNaOH，再回流2h，冷却后出料，通过2％的NaOH水溶液洗涤后分液得到产品2，4-二氯代苯丙基醚19g，产品经气相色谱分析纯度97％，得率90.1％。Get 16.5g of 2,4-dichlorophenol, 10g of NaOH, and 0.16g of triethylbenzyl ammonium chloride into the reactor, and add 36ml of water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 2,4-dichlorophenol, and when the temperature rises to 105°C, start to drop 26.8g of bromophenol through the dropping funnel. Add n-propane dropwise after 1 hour, the reaction temperature is about 95°C, reflux for 3 hours, then add 2g of NaOH, and then reflux for 2 hours, discharge after cooling, wash with 2% NaOH aqueous solution and separate to obtain the product 2,4- Dichlorophenylpropyl ether 19g, product purity 97% through gas chromatography, yield 90.1%.
使用有机溶剂用相转移催化合成二卤代芳香醚的对比实验：取2，4-二氯代苯酚16.5g，NaOH 6g，十六烷基三甲基溴化铵0.08g加入反应器中，加入25ml环己烷和5ml水。在反应器上安上回流冷凝管、搅拌装置、滴液装置和温度计，加热并使2，4-二氯代苯酚溶解，升温到溶剂回馏时，温度达75℃，开始通过滴液漏斗滴加25g溴代异丙烷，1h后滴加完毕，反应温度在65℃左右，回流反应10h，然后补加0.5gNaOH，再回流2h，冷却后分液，有机层通过2％的NaOH水溶液洗涤后，再蒸馏除去溶剂环己烷，得到油状产品2，4-二氯代苯丙基醚15g，产品经气相色谱分析纯度75％，得率55％左右。A comparative experiment of using organic solvents to synthesize dihalogenated aromatic ethers by phase transfer catalysis: Take 16.5g of 2,4-dichlorophenol, 6g of NaOH, and 0.08g of cetyltrimethylammonium bromide into the reactor, add 25ml cyclohexane and 5ml water. Install a reflux condenser, a stirring device, a dripping device and a thermometer on the reactor, heat and dissolve 2,4-dichlorophenol, when the temperature rises to 75°C when the solvent is distilled back, start to drop through the dropping funnel Add 25g of bromoisopropane, drop it after 1h, the reaction temperature is about 65°C, reflux for 10h, then add 0.5gNaOH, and then reflux for 2h, separate the liquid after cooling, and wash the organic layer with 2% NaOH aqueous solution, The solvent cyclohexane was then distilled off to obtain 15 g of oily product 2,4-dichlorophenylpropyl ether. The product was analyzed by gas chromatography with a purity of 75% and a yield of about 55%.
上述使用有机溶剂进行相转移催化合成二卤代芳香醚的实验中，由于有机溶剂与水产生共沸现象，使反应温度偏低，影响了反应活性。而本发明只用水作溶剂，解决了反应温度和活性的问题，同时简化了工艺，又减少了环境污染。In the experiment of using an organic solvent for phase transfer catalytic synthesis of dihalogenated aromatic ethers, the reaction temperature was low due to the azeotropic phenomenon between the organic solvent and water, which affected the reaction activity. However, the present invention only uses water as a solvent, which solves the problems of reaction temperature and activity, simplifies the process, and reduces environmental pollution.
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