CN1216024C - Preparing-1-pentanal from mixed solvent ion liquid of tetrafluorborate methyl buty I imidazole salt/water - Google Patents
Preparing-1-pentanal from mixed solvent ion liquid of tetrafluorborate methyl buty I imidazole salt/water Download PDFInfo
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- CN1216024C CN1216024C CN 200410017744 CN200410017744A CN1216024C CN 1216024 C CN1216024 C CN 1216024C CN 200410017744 CN200410017744 CN 200410017744 CN 200410017744 A CN200410017744 A CN 200410017744A CN 1216024 C CN1216024 C CN 1216024C
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Abstract
The present invention relates to a method for preparing 1-valeraldehyde by the hydroformylation reaction in mixed solvents preprared from ionic liquid fluoroboric acid methylbutyl imidazole salt-<Bmin> BF4 and water, which belongs to the technical field of organic compound preparation. In the method, in a mixed solvent prepared from <Bmin> BF4 and water, under the catalysis of rhodium trichloride and triphenylphosphino-m-trisulfonic sodium, 1-butene, CO and H2 are treated by hydroformylation reaction, then gravity settling and skimming to be prepared into product 1-valeraldehyde. The present invention has the advantages of high yield and selectivity, friendly environment, simple process, etc. The product prepared in the method is suitable for the production of perfume intermediate bodies, 1-valeric acid and other fine chemicals.
Description
Technical field
The present invention relates to a kind of at ionic liquid Tetrafluoroboric acid methyl butyl imidazole salts ([Bmim] BF
4Preparation 1-valeral promptly relates to a kind of method for preparing the 1-valeral in ionic liquid Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent in the)/water mixed solvent, belongs to the organic compound preparing technical field.
Background technology
The 1-valeral is called valeraldehyde again, is a kind of broad-spectrum chemical intermediate, and important purposes is especially arranged in the spices production.The 1-valeral is made through hydroformylation reaction by 1-butylene mostly at present, is expressed as with equation:
Because this reaction generates valeraldehyde and isovaleric aldehyde simultaneously, and the isomers isovaleric aldehyde of valeraldehyde, economic worth is much smaller comparatively speaking.Therefore improve that the ratio of valeraldehyde is one of main improvement direction of this technology of preparing in the product.
Hydroformylation reaction is used cobalt-carbonyl catalysis in early days, discovers that afterwards the catalytic performance of rhodium is more superior than cobalt.The sixties, along with developing rapidly of coordination chemistry, people begin organophosphorus ligand is applied to hydroformylation reaction.The application of organophosphorus ligand can increase the stability of catalyzer, reduces reaction pressure, and can improve selectivity of catalyst, suppresses side reaction, improves the ratio of linear product.But, easy separate and the recycle of catalyzer is a subject matter in the homogeneous phase hydroformylation course of industrialization of realizing catalyzer and product.
In order to overcome these problems, people have been developed water/organic biphasic catalysis reaction system, also developed and be applied to the water-soluble good of biphasic catalysis system and be insoluble to organic metal complex catalysts, but because catalyzer and raw material are in respectively in the immiscible two-phase, speed of response has been subjected to the restriction of two alternate mass transfer difficulties.The Li Xian equalization has been summed up improved catalysis long-chain olefin hydroformylation in " chemical progress 1998; 10; 146 " paper two-phase reaction system; as the biphasic catalysis system of adding cosolvent, nicellar catalysis system, supramolecule catalyst system; the temperature control phase transfer catalysis system; and the interface catalyst system etc., but these improved catalyst system have also increased the loss of rhodium catalyst or the separating difficulty of product when having increased speed of response.Therefore, water/organic biphasic catalysis reaction system can not well solve the loss and the speed of reaction problem on the low side of catalyzer simultaneously.
Ionic liquid is a class novel material of greatly being paid close attention in recent years, have good stability, non-volatile, with advantages such as the intermiscibility of organism or water is adjustable.Hydroformylation reaction in the ionic liquid has some reports.People such as Yves.Chauvind are applied to the 1-amylene hydroformylation reaction in the alkyl substituted imidazole salt ionic liquid with rhodium/triphenylphosphine sodium trisulfonate (Rh/TPPTS) type catalyzer, preparation 1-valeral.This preparation method's poor selectivity, product just/different ratio only is 2～4.
Summary of the invention
Advantages such as the technical problem to be solved in the present invention is to propose a kind of method for preparing the 1-valeral in ionic liquid Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent, and this method has the transformation efficiency height, and selectivity is good, and environmental friendliness and technology are simple.The present invention solves this technical problem by the following technical programs: in Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent, with Trichlororhodium (RhCl
3) and a triphenylphosphine sodium trisulfonate be catalyzer, 1-butylene makes product 1-valeral through step hydroformylation reaction, a gravity settling, separatory.
Now describe technical scheme of the present invention in detail.A kind of method for preparing the 1-valeral in ionic liquid Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent is characterized in that, concrete preparation process:
The first step hydroformylation reaction
Trichlororhodium with 1 part of weight, triphenylphosphine sodium trisulfonate between 200～220 parts of weight, the Tetrafluoroboric acid methyl butyl imidazole salts of 300 parts of weight and the water of 100 parts of weight are mixed into ionic liquid/water/catalyst system, inject the 1-butylene of 250 parts of weight and feed CO and H to this system
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 20～30 hours under 60～80 normal atmosphere, 80～100 ℃ and powerful the stirring;
The second step gravity settling, separatory
The reaction solution of the first step gained is cooled to room temperature, emits residual gas, gravity settling, supernatant liquid is isolated in product and ionic liquid/water/catalyst system layering, makes product, and wherein 1-valeral content is 86%～92%.
The yield of the 1-valeral of method preparation of the present invention is 80%～99%.
Technical scheme of the present invention is further characterized in that, isolated lower floor ionic liquid/water in second step/catalyst system circulation is used for the hydroformylation reaction of the first step.
The chemical reaction skeleton symbol relevant with above-mentioned preparation method is expressed as:
Compare with background technology, the present invention has the following advantages:
1. selectivity is good, just/different ratio is 9, and speed of reaction is higher, the reaction times shortens.
2. overcome the losing issue of catalyzer Trichlororhodium and triphenylphosphine sodium trisulfonate in the background technology, catalyzer is fixed in ionic liquid/water mixed system, thereby realizes recycling of catalyst system.
3. technology is simple, and the reaction solution of gained only needs separatory behind the gravity settling, can obtain high-quality product.
Embodiment
Embodiment 1
Drop into Trichlororhodium 1.0g in the autoclave pressure successively, a triphenylphosphine sodium trisulfonate 220g, Tetrafluoroboric acid methyl butyl imidazole salts 300g, water 100g and 1-butylene 250g feed CO and H
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 30 hours under 60 normal atmosphere, 80 ℃ and powerful the stirring, cooling, venting, gravity settling, separatory, product, yield 98%, wherein 1-valeral content 92%.Isolated ionic liquid/water catalyst system recycles.
Embodiment 2
Drop into Trichlororhodium 1.0g in the autoclave pressure successively, a triphenylphosphine sodium trisulfonate 220g, Tetrafluoroboric acid methyl butyl imidazole salts 300g, water 100g and 1-butylene 250g feed CO and H
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 20 hours under 60 normal atmosphere, 80 ℃ and powerful the stirring, cooling, venting, gravity settling, separatory, product, yield 80%, wherein 1-valeral content 92%.Isolated ionic liquid/water catalyst system recycles.
Embodiment 3
Drop into Trichlororhodium 1.0g in the autoclave pressure successively, a triphenylphosphine sodium trisulfonate 200g, Tetrafluoroboric acid methyl butyl imidazole salts 300g, water 100g and 1-butylene 250g feed CO and H
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 30 hours under 60 normal atmosphere, 80 ℃ and powerful the stirring, cooling, venting, gravity settling, separatory, product, yield 90%, wherein 1-valeral content 86%.Isolated ionic liquid/water catalyst system recycles.
Embodiment 4
Drop into Trichlororhodium 1.0g in the autoclave pressure successively, a triphenylphosphine sodium trisulfonate 220g, Tetrafluoroboric acid methyl butyl imidazole salts 300g, water 100g and 1-butylene 250g feed CO and H
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 20 hours under 80 normal atmosphere, 100 ℃ and powerful the stirring, cooling, venting, gravity settling, separatory, product, yield 95%, wherein 1-valeral content 91%.Isolated ionic liquid/water catalyst system recycles.
The present invention is specially adapted to the preparation 1-valeral of high yield and highly selective, is applicable to prepared in laboratory and industrial-scale production, and realizes cleaning of production.This product can be used for producing the 1-valeric acid, also can be used as the intermediate of synthetic other spices.
Claims (3)
1. method that in ionic liquid Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent, prepares the 1-valeral; it is characterized in that; in Tetrafluoroboric acid methyl butyl imidazole salts/water mixed solvent; with a Trichlororhodium and a triphenylphosphine sodium trisulfonate is catalyzer; 1-butylene makes product 1-valeral through a step hydroformylation reaction, gravity settling, separatory.
2. a kind of method for preparing the 1-valeral according to claim 1 is characterized in that, concrete preparation process:
The first step hydroformylation reaction
Trichlororhodium with 1 part of weight, triphenylphosphine sodium trisulfonate between 200～220 parts of weight, the Tetrafluoroboric acid methyl butyl imidazole salts of 300 parts of weight and the water of 100 parts of weight are mixed into ionic liquid/water/catalyst system, inject the 1-butylene of 250 parts of weight and feed CO and H to this system
2Volume ratio is 1: 1 a gas mixture, carries out hydroformylation reaction 20～30 hours under 60～80 normal atmosphere, 80～100 ℃ and powerful the stirring;
The second step gravity settling, separatory
The reaction solution of the first step gained is cooled to room temperature, emits residual gas, gravity settling, supernatant liquid is isolated in product and ionic liquid/water/catalyst system layering, makes product, and wherein 1-valeral content is 86%～92%.
3. a kind of method for preparing the 1-valeral according to claim 2 is characterized in that, isolated lower floor ionic liquid/water in second step/catalyst system circulation is used for the hydroformylation reaction of the first step.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410017744 CN1216024C (en) | 2004-04-16 | 2004-04-16 | Preparing-1-pentanal from mixed solvent ion liquid of tetrafluorborate methyl buty I imidazole salt/water |
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| CN 200410017744 CN1216024C (en) | 2004-04-16 | 2004-04-16 | Preparing-1-pentanal from mixed solvent ion liquid of tetrafluorborate methyl buty I imidazole salt/water |
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| CN1562932A CN1562932A (en) | 2005-01-12 |
| CN1216024C true CN1216024C (en) | 2005-08-24 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260147B (en) * | 2011-06-01 | 2013-11-06 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
| CN102658205B (en) * | 2012-04-19 | 2014-10-15 | 华东师范大学 | Catalyst for producing aldehyde through hydroformylation of alkene and application thereof |
| CN112479838A (en) * | 2020-12-02 | 2021-03-12 | 山东卓俊实业有限公司 | Application of imidazole carbonate in preparation of chemical intermediates |
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