CN100345806C - Method for preparing chloromethyl substituted arene - Google Patents
Method for preparing chloromethyl substituted arene Download PDFInfo
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- CN100345806C CN100345806C CNB2006100496661A CN200610049666A CN100345806C CN 100345806 C CN100345806 C CN 100345806C CN B2006100496661 A CNB2006100496661 A CN B2006100496661A CN 200610049666 A CN200610049666 A CN 200610049666A CN 100345806 C CN100345806 C CN 100345806C
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- CN
- China
- Prior art keywords
- substituted arene
- chloromethyl substituted
- arene
- methylene dichloride
- methylene chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 20
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 9
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- -1 boracic acid 1-ethyl-3-methylimidazole salts Chemical class 0.000 abstract 1
- 229960002645 boric acid Drugs 0.000 abstract 1
- 235000010338 boric acid Nutrition 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000002608 ionic liquid Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BETNPSBTDMBHCZ-UHFFFAOYSA-N 1-(chloromethyl)-2,4-dimethylbenzene Chemical compound CC1=CC=C(CCl)C(C)=C1 BETNPSBTDMBHCZ-UHFFFAOYSA-N 0.000 description 1
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- HKCWYAWNOIYUAS-UHFFFAOYSA-N 2,4-bis(chloromethyl)-1-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1CCl HKCWYAWNOIYUAS-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for preparing chloromethyl substituted arene, which comprises the following steps: step 1, arene, paraformaldehyde, hydrochloric acid with the weight concentration of 35% and tetrafluoro boracic acid 1-ethyl-3-methylimidazole salts which are used as catalysts are mixed according to a molar ratio of 1:1.5 to 2.5:12 to 15:0.1 to 0.5, and the reaction lasts at least for 5 hours under a stir condition under ordinary pressure and at the temperature of 50 to 90 DEG C; step 2, the reaction liquid is cooled to a room temperature and then is dissolved in methylene chloride for extraction layering, the methylene chloride layer is orderly washed by saturated sodium bicarbonate solution and water solution, methylene chloride is distilled under a pressure reducing condition, and chloromethyl substituted arene is obtained. The method of the present invention has the advantages of simple technologies, short reaction time, high yield, environmental protection and high quality of products, and is suitable for industrial scale production. The yield of the method of the present invention reaches 76 to 97%.
Description
Technical field
The present invention relates to prepare the method for chloromethyl substituted arene, belong to the organic compound preparing technical field.
Background technology
Chloromethyl substituted arene has important use in medicine and polymkeric substance process industry.The existing method for preparing chloromethyl substituted arene adopts acidic substance such as zinc chloride, tin tetrachloride etc. to make catalyzer mostly, realizes with aromatic hydrocarbons, Paraformaldehyde 96 and hydrochloric acid reaction.
Recently, also the fluorochemical of useful rare earth metal prepares chloromethyl substituted arene as catalyzer, though the use of these catalyzer can be shortened the reaction times greatly, improve reaction yield, such catalyzer cost height is not suitable for suitability for industrialized production.Prior preparation method also can not realize making environment, efficient and three indexs of yield to reach high level simultaneously.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, the method for preparing chloromethyl substituted arene of environmental friendliness and high yield.
The method for preparing chloromethyl substituted arene of the present invention, its step is as follows:
1) hydrochloric acid and the catalyzer Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt 1: 1.5 in molar ratio～2.5: 12～15: 0.1～0.5 of aromatic hydrocarbons, Paraformaldehyde 96, weight concentration 35% are mixed, under normal pressure, 50～90 ℃ and agitation condition, reacted at least 5 hours;
2) above-mentioned reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, and decompression steams methylene dichloride, obtains chloromethyl substituted arene.
Among the present invention, said aromatic hydrocarbons is benzene, toluene, o-Xylol, m-xylene, p-Xylol or methyl-phenoxide.
In order to save production cost, reduce environmental pollution, the further feature of the present invention is that catalyzer Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt is reclaimed the building-up reactions that circulation is used for the first step.
Chemical reaction skeleton symbol of the present invention is expressed as follows:
Beneficial effect of the present invention is:
1. be catalyzer with Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt, environmental friendliness, cheap and easy to get, can be recycled again, be applicable to industrial scale production.
2. technology is simple, and the reaction times is short, yield is high, and reaction only needs extracting and demixing, and underpressure distillation can obtain high-quality product.Productive rate can reach 76～97%.
Embodiment
Embodiment 1
With 127.9g benzene and 116g Paraformaldehyde 96, the concentrated hydrochloric acid of 1600mL 35%, 96g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, 70 ℃ and powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 76%, wherein chloromethylbenzene 17%, to xylylene dichlorides 59%.Can directly recycle after the ionic liquid drying in the water layer.
Embodiment 2
With 150.88g toluene and 79g Paraformaldehyde 96, the concentrated hydrochloric acid of 1368mL 35%, 32g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, under 90 ℃ and the powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 97%, 1-chloromethyl-2-methylbenzene 7% wherein, 1-chloromethyl-4-methylbenzene 28%, 1,3-dichloromethyl-4-methylbenzene 62%.Can directly recycle after the ionic liquid drying in the water layer.
Embodiment 3
With 174g o-Xylol and 131g Paraformaldehyde 96, the concentrated hydrochloric acid of 1710mL 35%, 160g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, under 50 ℃ and the powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 91%, 1-chloromethyl-3 wherein, 4-dimethyl benzene 19%, 1,2-chloromethyl-4,5-dimethyl benzene 72%.Can directly recycle after the ionic liquid drying in the water layer.
Embodiment 4
With 174g m-xylene and 106g Paraformaldehyde 96, the concentrated hydrochloric acid of 1500mL 35%, 128g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, under 60 ℃ and the powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 93%, wherein 1,5-chloromethyl-2,4-dimethyl benzene 85%, 1-chloromethyl-2,4-dimethyl benzene 8%.Can directly recycle after the ionic liquid drying in the water layer.
Embodiment 5
With 174g p-Xylol and 116g Paraformaldehyde 96, the concentrated hydrochloric acid of 1600mL 35%, 96g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, under 70 ℃ and the powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 90%, 1-chloromethyl-2 wherein, 5-dimethyl benzene 41%, 1,4-dichloromethyl-2,5-dimethyl 49%.Can directly recycle after the ionic liquid drying in the water layer.
Embodiment 6
With 177g methyl-phenoxide and 116g Paraformaldehyde 96, the concentrated hydrochloric acid of 1600mL 35%, 96g ionic liquid Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt mixes, and under normal pressure, under 70 ℃ and the powerful stirring condition, reacts 5 hours; Reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, and dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, just obtains product after decompression steams methylene dichloride.Transformation efficiency 90%, 1-methoxyl group-4-chloromethylbenzene 17% wherein, 1-methoxyl group-2,4-xylylene dichlorides 73%.Can directly recycle after the ionic liquid drying in the water layer.
Claims (2)
1. the method for preparing chloromethyl substituted arene, its step is as follows:
1) hydrochloric acid and the catalyzer Tetrafluoroboric acid 1-ethyl-3-methylimidazole salt 1: 1.5 in molar ratio～2.5: 12～1 5: 0.1～0.5 of aromatic hydrocarbons, Paraformaldehyde 96, weight concentration 35% are mixed, under normal pressure, 50～90 ℃ and agitation condition, reacted at least 5 hours;
2) above-mentioned reaction solution is cooled to room temperature, is dissolved in methylene dichloride, extracting and demixing, dichloromethane layer is used saturated sodium bicarbonate aqueous solution and water washing successively, and decompression steams methylene dichloride, obtains chloromethyl substituted arene.
2. the method for preparing chloromethyl substituted arene according to claim 1 is characterized in that said aromatic hydrocarbons is benzene, toluene, o-Xylol, m-xylene, p-Xylol or methyl-phenoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100496661A CN100345806C (en) | 2006-03-02 | 2006-03-02 | Method for preparing chloromethyl substituted arene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100496661A CN100345806C (en) | 2006-03-02 | 2006-03-02 | Method for preparing chloromethyl substituted arene |
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| Publication Number | Publication Date |
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| CN1814578A CN1814578A (en) | 2006-08-09 |
| CN100345806C true CN100345806C (en) | 2007-10-31 |
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| CNB2006100496661A Expired - Fee Related CN100345806C (en) | 2006-03-02 | 2006-03-02 | Method for preparing chloromethyl substituted arene |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381362B (en) * | 2008-10-13 | 2012-10-31 | 广东工业大学 | Preparation method of thiophen derivate chloromethylation products |
| CN110028379B (en) * | 2019-04-04 | 2022-03-18 | 三峡大学 | Preparation method of 4, 4' -dichloromethyl biphenyl |
| CN111362776A (en) * | 2020-04-25 | 2020-07-03 | 河北兰升生物科技有限公司 | Improved preparation method of 2, 5-disubstituted benzyl chloride |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
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2006
- 2006-03-02 CN CNB2006100496661A patent/CN100345806C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 1-乙基-3-甲基咪唑四氟硼酸盐的量子化学研究 刘坤辉等人，化学物理学报，第18卷第3期 2005 * |
| 室温离子液中芳香族亲核取代反应的研究 郑云法等人，浙江大学学报(理学版)，第32卷第3期 2005 * |
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| CN1814578A (en) | 2006-08-09 |
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Granted publication date: 20071031 Termination date: 20100302 |