CN103242153A - Method for catalyzing preparation of benzoin from benzaldehyde by adopting imidazolium bicarbonate ionic liquid - Google Patents
Method for catalyzing preparation of benzoin from benzaldehyde by adopting imidazolium bicarbonate ionic liquid Download PDFInfo
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 244000028419 Styrax benzoin Species 0.000 title claims abstract description 23
- 235000000126 Styrax benzoin Nutrition 0.000 title claims abstract description 23
- 235000008411 Sumatra benzointree Nutrition 0.000 title claims abstract description 23
- 229960002130 benzoin Drugs 0.000 title claims abstract description 23
- 235000019382 gum benzoic Nutrition 0.000 title claims abstract description 23
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 21
- GYTMUNSNMBRSEW-UHFFFAOYSA-N hydrogen carbonate;1h-imidazol-1-ium Chemical compound OC(O)=O.C1=CNC=N1 GYTMUNSNMBRSEW-UHFFFAOYSA-N 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 8
- JCSHYFOSLVIDGY-UHFFFAOYSA-N imidazol-1-yl hydrogen carbonate Chemical compound OC(=O)ON1C=CN=C1 JCSHYFOSLVIDGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 1,3-dibutylimidazole bicarbonate Chemical compound 0.000 description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007193 benzoin condensation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CFCNWHQKGUZEDB-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;hydrogen carbonate Chemical compound OC([O-])=O.CN1C=C[N+](C)=C1 CFCNWHQKGUZEDB-UHFFFAOYSA-M 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- JIKBCEMIKSCAKL-UHFFFAOYSA-N acetic acid;2-hydroxy-1,2-diphenylethanone Chemical class CC(O)=O.C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 JIKBCEMIKSCAKL-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 239000002699 waste material Substances 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
一种采用咪唑碳酸氢盐离子液体作为催化剂催化苯甲醛制备安息香的方法，它是将苯甲醛加入到四氢呋喃中，加入相当于苯甲醛摩尔量2%～15%的咪唑碳酸氢盐离子液体催化剂（IL-Cat），在室温～80℃间，反应4h，然后，减压蒸馏，除去反应溶剂得到白色固体，加入蒸馏水使固体分散，过滤得滤饼，60℃真空干燥8h，即得到安息香。本发明方法温和高效、反应产率和选择性都很高。与已有使用离子液体的方法相比，由于使用本发明的方法无需加入任何碱性物质，本发明的方法将更加的经济、环保。A method for preparing benzoin by using imidazole bicarbonate ionic liquid as catalyst to catalyze benzaldehyde, which is to add benzaldehyde into tetrahydrofuran, and add imidazole bicarbonate ionic liquid catalyst ( IL-Cat), react at room temperature to 80°C for 4 hours, then distill under reduced pressure to remove the reaction solvent to obtain a white solid, add distilled water to disperse the solid, filter to obtain a filter cake, and vacuum dry at 60°C for 8 hours to obtain benzoin. The method of the invention is mild and efficient, and has high reaction yield and selectivity. Compared with the existing method of using ionic liquid, since the method of the invention does not need to add any alkaline substances, the method of the invention will be more economical and environmentally friendly.
Description
技术领域technical field
本发明涉及一种用咪唑碳酸氢盐离子液体催化苯甲醛制备安息香的方法。The invention relates to a method for preparing benzoin by using imidazole bicarbonate ionic liquid to catalyze benzaldehyde.
背景技术Background technique
安息香是一种重要的化工原料，广泛用作感光性树脂的光敏剂、染料中间体和粉末涂料的防缩孔剂，也是一种重要的药物合成中间体，如抗癫痫药物二苯基乙内酰脲的合成以及二苯基乙二酮、二苯基乙二酮肟、乙酸安息香类化合物。安息香可以苯甲醛通过安息香缩合或苯偶姻反应制备。经典的安息香合成以氰化钠或氰化钾为催化剂（organicreaction，1948，(4)：269），虽然产率高,但毒性很大,既破坏环境,又影响健康，新改进的方法使用具有生物活性的辅酶维生素B1为催化剂，该方法具有操作简单，节省原料，耗时短，污染轻等特点。但是反应需要在冰水浴中操作，而且反应收率往往比较低，催化剂价格昂贵，不便于回收(大学化学,2001,16(3):49～50.)。也有报道使用卡宾为催化剂来催化苯甲醛制备安息香（DE19704273-A1），但卡宾催化剂价格昂贵且结构不稳定使得相应方法难以实现工业化。最近几年开始出现使用离子液体为催化剂来制备安息香，（CN102153525-A、Chem.Lett.2005，16(3)，321、J.Mol.Catal.A:Chem.2006，256,，261、Tetrahedron Lett.2007，48，755和有机化学，2010，30（6），912～917），但是在所有已知的离子液体催化苯甲醛制备安息香的反应中都必须加入大量的强碱性物质（如叔丁醇钾、氢化钠、碳酸铯、氢氧化钾、碳酸钾等），这些强碱性物质的加入具有三个方面的缺陷：（1）对反应设备提出了更高的要求；（2）增加了原料成本；（3）反应后会产生大量废弃物。Benzoin is an important chemical raw material, widely used as a photosensitizer for photosensitive resins, a dye intermediate and an anti-cratering agent for powder coatings. Synthesis of ureides and diphenyl ketone, diphenyl ketone oxime, acetic acid benzoin compounds. Benzoin can be prepared from benzaldehyde by benzoin condensation or benzoin reaction. The classic synthesis of benzoin uses sodium cyanide or potassium cyanide as a catalyst (organicreaction, 1948, (4): 269). Although the yield is high, it is very toxic, which not only damages the environment, but also affects health. The new improved method uses The biologically active coenzyme vitamin B1 is used as a catalyst, and the method has the characteristics of simple operation, saving raw materials, short time consumption, light pollution and the like. However, the reaction needs to be operated in an ice-water bath, and the reaction yield is often relatively low, and the catalyst is expensive and not easy to recycle (University Chemistry, 2001, 16(3): 49-50.). It is also reported to use carbene as catalyst to catalyze benzaldehyde to prepare benzoin (DE19704273-A1), but the expensive and unstable structure of carbene catalyst makes it difficult to realize the industrialization of the corresponding method. Begin to use ionic liquid to prepare benzoin in recent years as catalyst, (CN102153525-A, Chem.Lett.2005, 16 (3), 321, J.Mol.Catal.A:Chem.2006, 256,, 261, Tetrahedron Lett.2007, 48, 755 and Organic Chemistry, 2010, 30 (6), 912～917), but in all known ionic liquid catalyzed reactions of preparing benzoin from benzaldehyde, a large amount of strong alkaline substances must be added (such as Potassium tert-butoxide, sodium hydride, cesium carbonate, potassium hydroxide, potassium carbonate, etc.), the addition of these strong alkaline substances has three defects: (1) higher requirements are placed on the reaction equipment; (2) Raw material cost is increased; (3) A large amount of waste will be generated after the reaction.
发明内容Contents of the invention
本发明的目的是提供一种全新的采用咪唑碳酸氢盐离子液体作为催化剂催化苯甲醛制备安息香的方法。与所有采用离子液体为催化剂的方法不同的是：该方法采用咪唑碳酸氢盐离子液体作为催化剂，使用该催化剂催化苯甲醛制备安息香不需加入任何碱性物质即可获得非常满意的产率。该催化剂制备方法简单，廉价易得，反应条件温和，安息香的产率和选择性都很高，几乎无副反应发生。反应后可以简单的通过水洗的方法从反应体系中回收得到咪唑碳酸氢盐离子液体催化剂。The purpose of the present invention is to provide a kind of brand-new adopting imidazolium bicarbonate ionic liquid to prepare the method for benzoin by catalyzing benzaldehyde as catalyst. Different from all methods using ionic liquids as catalysts, this method uses imidazolium bicarbonate ionic liquids as catalysts, and using this catalyst to catalyze benzaldehyde to prepare benzoin can obtain a very satisfactory yield without adding any alkaline substances. The preparation method of the catalyst is simple, cheap and easy to obtain, mild reaction conditions, high yield and selectivity of benzoin, and almost no side reaction. After the reaction, the imidazolium bicarbonate ionic liquid catalyst can be simply recovered from the reaction system by washing with water.
在本发明之前，在不加入强碱性物质的情况下，使用离子液体为催化剂催化苯甲醛制备安息香是完全不可能的。Before the present invention, it was completely impossible to prepare benzoin by using ionic liquid as a catalyst to catalyze benzaldehyde without adding strong alkaline substances.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种采用咪唑碳酸氢盐离子液体作为催化剂催化苯甲醛制备安息香的方法，其反应式如下：A kind of method that adopts imidazolium bicarbonate ionic liquid to prepare benzoin as catalyst catalysis benzaldehyde, its reaction formula is as follows:
它包括如下步骤：It includes the following steps:
将苯甲醛加入到四氢呋喃（THF）中，加入相当于苯甲醛摩尔量2%～15%的咪唑碳酸氢盐离子液体催化剂（IL-Cat），在室温～80℃间，优选50℃～70℃，反应4h，然后，减压蒸馏，除去反应溶剂得到白色固体，加入蒸馏水使固体分散，过滤得滤饼，60℃真空干燥8h，即可得到安息香。Add benzaldehyde to tetrahydrofuran (THF), add imidazolium bicarbonate ionic liquid catalyst (IL-Cat) equivalent to 2% to 15% of the molar weight of benzaldehyde, at room temperature to 80°C, preferably 50°C to 70°C , reacted for 4h, and then distilled under reduced pressure to remove the reaction solvent to obtain a white solid, add distilled water to disperse the solid, filter to obtain a filter cake, and vacuum dry at 60°C for 8h to obtain benzoin.
上述制备安息香方法所使用的催化剂IL-Cat为咪唑碳酸氢盐离子液体，其具有如下通式：[CmCn-IM][HCO3]，其结构式如下：The catalyst IL-Cat used in the above method for preparing benzoin is imidazolium bicarbonate ionic liquid, which has the following general formula: [C m C n -IM][HCO 3 ], and its structural formula is as follows:
其中Cm、Cn均为烷基取代基，Cm、Cn为甲基、乙基、丙基、丁基、己基或辛基中的一种，m、n分别代表取代基碳的个数。Among them, C m and C n are alkyl substituents, C m and Cn are one of methyl, ethyl, propyl, butyl, hexyl or octyl, and m and n respectively represent the number of substituent carbons .
一种制备上述的咪唑碳酸氢盐离子液体[CmCn-IM][HCO3]方法如下：A method for preparing the above-mentioned imidazolium bicarbonate ionic liquid [CmCn-IM] [HCO 3 ] is as follows:
将所要制备的咪唑碳酸氢盐离子液体所对应的咪唑氯盐（[CmCn-IM][Cl]）加入到适当甲醇溶剂中，加入咪唑氯盐摩尔量1.1倍的碳酸氢钾或碳酸氢钠，室温下搅拌反应48h，反应结束后，过滤除去钾盐或钠盐，蒸干滤液，80℃真空干燥24h，得到咪唑碳酸氢盐离子液体。Add the imidazolium chloride salt ([CmCn-IM][Cl]) corresponding to the imidazolium bicarbonate ionic liquid to be prepared into an appropriate methanol solvent, and add potassium bicarbonate or sodium bicarbonate with 1.1 times the molar weight of the imidazolium chloride salt, The reaction was stirred at room temperature for 48 hours. After the reaction, the potassium salt or sodium salt was removed by filtration, the filtrate was evaporated to dryness, and vacuum-dried at 80° C. for 24 hours to obtain the imidazolium bicarbonate ionic liquid.
本发明不同于先前发明之处在于：该方法采用咪唑碳酸氢盐离子液体催化苯甲醛制备安息香，不需要加入任何碱性物质。该方法使用的咪唑碳酸氢盐制备方法简单，廉价易得，可溶于常规有机溶剂，又在水中具有较好的溶解度，而且在水中的溶解度往往大于在有机溶剂中的溶解度。使得反应过程中咪唑碳酸氢盐离子液体催化剂可以很好的溶解于反应体系，而在反应结束后通过简单的水洗的方法便可以从反应体系中除去催化剂，然后再蒸除水分，即可回收得到催化剂的。The present invention is different from the previous invention in that: the method adopts imidazolium bicarbonate ionic liquid to catalyze benzaldehyde to prepare benzoin without adding any alkaline substance. The preparation method of the imidazole bicarbonate used in the method is simple, cheap and easy to obtain, soluble in conventional organic solvents, and has good solubility in water, and the solubility in water is often greater than that in organic solvents. During the reaction process, the imidazolium bicarbonate ionic liquid catalyst can be well dissolved in the reaction system, and the catalyst can be removed from the reaction system by simple water washing after the reaction, and then evaporated to remove water, which can be recovered to obtain Catalyst.
具体实施方式Detailed ways
以下的实施例将对本发明进行更为全面的描述。The following examples will more fully describe the present invention.
实施例1Example 1
在150ml的茄形瓶中加入THF100mL，苯甲醛（0.2mol，21.224g），加入1,3-二丁基咪唑碳酸氢盐（[C4C4-IM][HCO3]）（0.02mol，4.846g），在80℃水浴下，反应4h。反应结束后蒸干溶剂，加入50g水搅拌10分钟，过滤出固体，真空烘干，得固体19.158g，熔点：135.5～137.8℃，产率90.26%Add THF100mL, benzaldehyde (0.2mol, 21.224g) into a 150ml eggplant-shaped bottle, add 1,3-dibutylimidazole bicarbonate ([C 4 C 4 -IM][HCO 3 ]) (0.02mol, 4.846g), under 80℃ water bath, react for 4h. After the reaction, evaporate the solvent to dryness, add 50g of water and stir for 10 minutes, filter out the solid, and dry in vacuum to obtain 19.158g of solid, melting point: 135.5-137.8°C, yield 90.26%
实施例2Example 2
在150ml的茄形瓶中加入THF100mL，苯甲醛（0.2mol，21.224g），加入1,3-二甲基咪唑碳酸氢盐（[C4C4-IM][HCO3]）（0.004mol，0.9692g），在50℃水浴下，反应4h。反应结束后蒸干溶剂，加入50g水搅拌10分钟，过滤出固体，真空烘干，得固体3.767g，熔点：136.3～137.9℃，产率17.75%Add THF100mL, benzaldehyde (0.2mol, 21.224g) into a 150ml eggplant-shaped bottle, add 1,3-dimethylimidazolium bicarbonate ([C 4 C 4 -IM][HCO 3 ]) (0.004mol, 0.9692g), reacted for 4h in a water bath at 50°C. After the reaction, evaporate the solvent to dryness, add 50g of water and stir for 10 minutes, filter out the solid, and dry in vacuum to obtain 3.767g of solid, melting point: 136.3～137.9°C, yield 17.75%
实施例3Example 3
在150ml的茄形瓶中加入THF100mL，苯甲醛（0.2mol，21.224g），加入1,3-二乙基咪唑碳酸氢盐（[C4C4-IM][HCO3]）（0.03mol，7.269g），在室温，反应4h。反应结束后蒸干溶剂，加入50g水搅拌10分钟，过滤出固体，真空烘干，得固体13.728g，熔点：136.3～137.6℃，产率64.68%Add THF100mL, benzaldehyde (0.2mol, 21.224g) into a 150ml eggplant-shaped bottle, add 1,3-diethylimidazole bicarbonate ([C 4 C 4 -IM][HCO 3 ]) (0.03mol, 7.269g), react at room temperature for 4h. After the reaction, evaporate the solvent to dryness, add 50g of water and stir for 10 minutes, filter out the solid, and dry in vacuum to obtain 13.728g of solid, melting point: 136.3～137.6°C, yield 64.68%
实施例4～14Embodiment 4～14
方法类似实施例1，采用不同的咪唑碳酸氢盐离子液体作为催化剂，结果见表1：Method is similar to embodiment 1, adopts different imidazolium bicarbonate ionic liquids as catalyst, and the results are shown in Table 1:
表1Table 1
对比实施例15～22Comparative Examples 15-22
为突出本发明与已有方法的不同之处，类似实施例1，采用非咪唑碳酸氢盐离子液体作为催化剂，结果见（表2），由表可见传统离子液体必须在加入强碱后，才能获得安息香产物。In order to highlight the difference between the present invention and the existing method, similar to Example 1, non-imidazole bicarbonate ionic liquid is used as the catalyst, the results are shown in (Table 2), it can be seen from the table that the traditional ionic liquid must be added after adding a strong base. Obtain benzoin product.
表2Table 2
备注：*表示该实施例中，加入催化剂时同时加入有机碱或者无机碱，加入碱的量为苯甲醛摩尔量的20%，其余反应条件和过程与实施例1相同。Remarks: * indicates that in this embodiment, an organic base or an inorganic base is added simultaneously when the catalyst is added, and the amount of the base added is 20% of the molar amount of benzaldehyde, and the rest of the reaction conditions and processes are the same as in Example 1.
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| CN109665953A (en) * | 2018-12-21 | 2019-04-23 | 盐城锦明药业有限公司 | A method of preparing styrax class compound |
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| JPS5780338A (en) * | 1980-11-07 | 1982-05-19 | Sumitomo Chem Co Ltd | Preparation of benzoin |
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| CN102702023A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Synthesis method of trans-alpha-benzoinoxime |
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