CN101857608A - Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification - Google Patents

Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification Download PDF

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CN101857608A
CN101857608A CN 201010194349 CN201010194349A CN101857608A CN 101857608 A CN101857608 A CN 101857608A CN 201010194349 CN201010194349 CN 201010194349 CN 201010194349 A CN201010194349 A CN 201010194349A CN 101857608 A CN101857608 A CN 101857608A
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diphenylphosphino
butyl
ionic liquid
radical
organophosphorus ligand
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张锁江
刁琰琰
李靖
闫瑞一
杨普
张香平
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Institute of Process Engineering of CAS
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Abstract

The invention describes an imidazole ionic liquid phosphine ligand with the structural formulas of (A) and (b) as shown in specification, wherein R represents H, alkyl, carboxyl or hydroxide radical; n is zero or a positive integer; and X- is BF4<->, PF6<->, Cl<->, Br<->, I<->, carboxylate radical or sulfonic acid anion. The invention also describes a metal complex catalyst system by using the imidazole ionic liquid as an organic phosphine ligand and a method for olefin hydoresterification by using the catalyst system. The method in the invention can improve commercial feasibility of the hydroesterification process.

Description

The application in hydroesterification reaction of imidazole ionic liquid phosphine ligand and title complex thereof
Technical field
The present invention relates to the synthetic of a kind of imidazole ion liquid type organic phosphine and be the metal complex catalyst system of organophosphorus ligand, and this catalyst body ties up to the application in the hydroesterification reaction of alkene and carbon monoxide and alcohols with this imidazole ion liquid.
Background technology
Pure and mild comprise the 8th, 9 or 10 family's metals for example the catalyst system of palladium and phosphine part for example alkylphosphines, cycloalkyl phosphine, aryl phosphine, pyridyl phosphine or bidentate phosphine in the presence of, use carbon monoxide to carry out the carbonylation of alefinically unsaturated compounds, in many patents, be described, for example EP-A-04489472, EP-A-0499329, EP-A-0495547, US2005085671A1, US6284919B1, US2001051745A1, US6476255B1, WO2007057640A1.Especially US6476255B1 discloses one group of bidentate phosphine thing with substituted aryl bridge can provide remarkable and must be higher than the speed of reaction of previous those disclosed catalyzer and produce a little or do not produce impurity, and has high conversion.
But, improving reaction-ure conversion-age by the mode that changes catalyst ligand in the above-mentioned patent, the bidentate phosphine part costs an arm and a leg and is extremely unstable in air; And the branched carboxylic acids ester that generates when used alkene is aryl olefin or long-chain fat alkene and the ratio of straight-chain carboxylic acid's ester are uncontrollable, and at these problems, existing patent does not all propose effective terms of settlement.
Have been found that now by in catalystic converter system, adding ionic liquid, can make catalyzer obtain better stability, and the higher TON of realization, be coordinated in the complex compound catalyst by further ionic liquid being made organophosphorus ligand, stable catalyst performance more be can obtain, and therefore the higher activity and the stereoselectivity of product realized.
Summary of the invention
The purpose of this invention is to provide the imidazole ion liquid organophosphorus ligand, with this organic phosphine ionic liquid metal complex catalyst system that is part and under this catalyst system the method for alkene hydroesterification reaction.
A first aspect of the present invention, it is (A) and imidazole ion liquid type organophosphorus ligand (B) that a kind of general formula is provided.
Figure BSA00000138465700021
Wherein R represents H, alkyl chain, carboxyl, hydroxyl; N is 0 or positive integer; X-is BF 4 -, PF 6 -, Cl -, Br -, I -, carboxylate radical, sulfonate radical negative ion; (A) and (B) ionic liquid of structural formula can be 1-(diphenylphosphino) ethyl-3-Methylimidazole bromine salt, 1-(diphenylphosphino) ethyl-3-methyl imidazolium tetrafluoroborate, 1-(diphenylphosphino) butyl-3-Methylimidazole bromine salt, 1-(diphenylphosphino) butyl-3-ethyl imidazol(e) hexafluoro phosphonate, 1-butyl-2-(diphenylphosphino)-3-Methylimidazole bromine salt, 1-butyl-2-(diphenylphosphino)-3-methyl imidazolium tetrafluoroborate, 1-butyl-2-(diphenylphosphino)-other ionic liquids such as 3-Methylimidazole hexafluoro phosphonate.
A second aspect of the present invention provides a kind of catalyst system of alkene hydroesterification reaction: the ionic liquid organophosphorus ligand can obtain metal complex by metal or the combination of its compound with the 8th, 9 and 10 families, forms a kind of catalyst system; Metal complex catalyst is ML nX mForm, wherein M is the 8th, 9 or 10 family's metals, preferable alloy Pd, Ru, Rh and Pt, more preferably Pd and Rh; L is the ion liquid type organophosphorus ligand; X is halogen, carbonate, bicarbonate radical, nitrate radical, carboxylate radical or sulfonate radical; N is the numerical value that is equal to or less than the metal-complexing number, and m is 1 or 2 and equal the oxidation state of metal.
A third aspect of the present invention provides a kind of method of alkene hydroesterification reaction, and it is included in imidazole ion liquid type organophosphorus ligand, acid source and metal complex catalyst and exists and make alkene and CO and alcohols react generation corresponding carboxylic acid ester down.Acid source can be one or more pKa that measure in dilute aqueous soln less than 5 acid.
Catalyst system of the present invention can homogeneous phase or heterogeneous use, and preferred homogeneous phase uses this catalyst system.Method of the present invention can be used for alkene hydroesterification in the presence of carbon monoxide and alcohol compound and optional negative ion source.Have been found that above-mentioned imidazole ion liquid organophosphorus ligand and metal complex catalyst system thereof have surprising raising activity of such catalysts and stability in hydroesterification reaction, the turnover number (TON) (product mole number/metal molar number) of hydroesterification reaction is greater than the turnover number of triphenylphosphine under the same terms usually.Above-mentioned reaction conditions is in batch reactions, and successive reaction can be more useful.Therefore, will improve the commercial viability of hydroesterification technology by method of the present invention.
Being fit to alkene of the present invention can be fatty alkene such as ethene, propylene, butylene, iso-butylene, amylene, also can be aromatic olefins such as vinylbenzene; Used alcohol can be aliphatic alcohols such as methyl alcohol, ethanol, propyl carbinol, the trimethyl carbinol, also can be aromatic series alcohols such as phenylcarbinol.
In the method for the invention, can in reaction, use the carbon monoxide of pure form; Perhaps be other gas of inert in the presence of use, the example of described gas comprises for example argon gas of nitrogen, carbonic acid gas and rare gas; Also can there be small amounts of hydrogen, typically less than the hydrogen of 5% volume.Gas feeds blistering reaction in the reaction system.
In the method for the invention, under 20～150 ℃ temperature, carry out hydroesterification reaction, preferably under 60～100 ℃ temperature, react.Pressure is 0.1～100MPa, preferred 1～10MPa.
In the method for the invention, time length of hydroesterification is had no particular limits, obviously preferably in commercial acceptable time scale, carry out.Hydroesterification in rhythmic reaction can take place maximum 50 hours, and at least 5 minutes, preferred 1～20 hour.
Specify the present invention with embodiment below, the transformation efficiency of alkene (or alcohols) and the selectivity gas Chromatographic Determination of carboxylicesters, it is defined as follows:
Figure BSA00000138465700031
Figure BSA00000138465700032
Figure BSA00000138465700033
Utilizing this ion liquid type organophosphorus ligand and catalyst system to prepare carboxylicesters compares with the preparation method that existing patent is mentioned, the good advantage of stereoselectivity with conversion of raw material height, product, the good stability of while catalyzer, consumption is few, and can be recycled.
Embodiment 1
The preparation of 1-(diphenylphosphino) ethyl-3-Methylimidazole bromine salt ion liquid organophosphorus ligand
Figure BSA00000138465700034
Synthesis step:
Add 0.2mol (37.57g) glycol dibromide and 20mL THF in the 150mL there-necked flask, logical nitrogen 20min, under 60 ℃, drip 0.2mol (16.40g) N-Methylimidazole gradually, dropwise in the 30min, continue reaction 3h, generate white precipitate, vacuum filtration and with THF washing 2 times, 80 ℃ of vacuum-drying 2h, white crystal (intermediate A), weighing gets product 49.34g, and yield is 91.14%.Add 100mL THF and 13.10g triphenylphosphine in the 250mL there-necked flask, logical nitrogen protection after the stirring and dissolving, adds 0.180g lithium sheet; react 4h down at 20 ℃, solution becomes orange, removes unreacted lithium sheet; add tert-butyl chloride 5mL then, reaction 30min filters.Add the white crystals product that the 13.30g the first step makes in the reaction solution, the orange of solution is taken off, and begins to become muddy, 30min final vacuum suction filtration, and 80 ℃ of vacuum-drying 2h get field gray product (target product) 27.40g, and yield is 90.5%.
Embodiment 2
The preparation of 1-(diphenylphosphino) ethyl-3-methyl imidazolium tetrafluoroborate ionic liquid organophosphorus ligand
Figure BSA00000138465700042
To synthesize BmimBF 4Raw material BmimBr (109.5g, 0.5mol) and NaBF 4(60.5g, 0.55mol) aqueous solution 150mL adding has in the there-necked flask of cooling for reflux, at N 2Protection is down in 40 ℃ of following stirring reaction 10h.Divide three times with methylene dichloride, each 60mL, the product that extractive reaction generates, total dichloromethane extraction liquid water be repeatedly washing on a small quantity, up to by AgNO3 (0.5mol/L) aqueous assay less than bromide anion till.The decompression rotary evaporation remove methylene dichloride obtain product (96.1g, 0.43mol), 70 ℃ of following vacuum-drying 24h.
Embodiment 3
The preparation of 1-(diphenylphosphino) butyl-3-Methylimidazole bromine salt ion liquid organophosphorus ligand
Figure BSA00000138465700043
Synthesis step just is replaced by 1 with the raw material glycol dibromide with embodiment 1, and the 2-dibromobutane gets 1-(diphenylphosphino) butyl-3-Methylimidazole bromine salt ion liquid part, and product yield is 88.7%.
Embodiment 4
The preparation of 1-(diphenylphosphino) butyl-3-ethyl imidazol(e) hexafluoro phosphonate ionic liquid organophosphorus ligand
Figure BSA00000138465700051
Synthesis step is with embodiment 2, just with raw material 1-(diphenylphosphino) ethyl-3-Methylimidazole bromine salt and NaBF 4The aqueous solution is replaced by 1-(diphenylphosphino) butyl-3-ethyl imidazol(e) bromine salt and KPF 6The aqueous solution gets 1-(diphenylphosphino) butyl-3-ethyl imidazol(e) hexafluoro phosphonate ionic liquid part, and product yield is 85.4%.
Embodiment 5
The preparation of 1-butyl-2-(diphenylphosphino)-3-methyl imidazolium tetrafluoroborate ionic liquid organophosphorus ligand
Figure BSA00000138465700052
Synthesis step:
Figure BSA00000138465700053
BmimBF with 3.0mmol 4Be dissolved in the 20ml methylene dichloride and (use P in advance 2O 5Dewater) in, under nitrogen protection, under-78 ℃, add 3.0mmol n-BuLi (in the normal hexane 15%) in the 15min, stir 45min afterwards.When mixture reaction is abundant, in 20min, add 3.0mmol Ph 2PCl, reactant progressively is heated to room temperature afterwards, spends the night.After this three equal parts distilled water purification by liquid extraction of solution after with the degassing got organic phase dry final vacuum to the anhydrous sodium sulphate and removed and desolvate, and obtains the beige solid precipitation, and be dry afterwards, preserves down in inert atmosphere, and product yield is 74.6%.
Embodiment 6
The preparation of 1-butyl-2-(diphenylphosphino)-3-ethyl imidazol(e) hexafluoro phosphonate ionic liquid organophosphorus ligand
Synthesis step is with embodiment 2, just with raw material 1-(diphenylphosphino) ethyl-3-Methylimidazole bromine salt and NaBF 4The aqueous solution is replaced by 1-butyl-2-(diphenylphosphino)-3-methyl imidazolium tetrafluoroborate and KPF 6The aqueous solution gets 1-butyl-2-(diphenylphosphino)-3-methyl imidazolium tetrafluoroborate ionic liquid part, and product yield is 87.7%.
Embodiment 7
With 0.0045g ((about 0.02mmol)) palladium, 0.14mmol different ionic liquid organic phosphine, (0.0173g about 0.18mmol) methylsulphonic acid, took off 60mL (about 0.51mol) vinylbenzene of gas, took off 90mL (about 2.23mol) methyl alcohol of gas, in glove box, join homemade 200mL and have the teflon-lined stainless steel reactor, from glove box, take out, feed CO gas (99.99% purity) to 1.0MPa.80 ℃ were reacted 3 hours down, and be chilled to room temperature and emit unreacted CO, the gas chromatographic analysis of the methyl phenylpropionate of preparation and 2-phenylpropionic acid methyl esters and unreacted reactant, experimental result sees Table 1.
Embodiment 8
With 0.0045g ((about 0.02mmol)) palladium, 0.14mmol different ionic liquid organic phosphine, (0.0173g about 0.18mmol) methylsulphonic acid, took off the 100mL methyl alcohol of gas, in glove box, join homemade 200mL and have the teflon-lined stainless steel reactor, from glove box, take out, feed the gas mixture (mol ratio is 1: 1) of ethene and carbon monoxide, be forced into 1.0MPa, temperature is to begin reaction under 80 ℃, logical continuously gas mixture reaction 3 hours, be chilled to room temperature, pressure is reduced to normal pressure, the gas chromatographic analysis of preparation methyl propionate, and experimental result sees Table 2.
Table 1 embodiment result
Figure BSA00000138465700071
Table 2 embodiment result
Phosphine part among the embodiment Methanol conversion (%) The selectivity of methyl propionate (%)
Embodiment 1 phosphine part ??65.2 ??99.1
Embodiment 2 phosphine parts ??67.8 ??98.9
Embodiment 3 phosphine parts ??69.6 ??99.5
Embodiment 4 phosphine parts ??66.1 ??99.6
Embodiment 5 phosphine parts ??62.4 ??99.3
Embodiment 6 phosphine parts ??63.2 ??99.4

Claims (4)

1. imidazole ion liquid type organophosphorus ligand, its structural formula is as follows:
Figure FSA00000138465600011
Wherein R represents H, alkyl, carboxyl, hydroxyl; N is 0 or positive integer; X-is BF 4 -, PF 6 -, Cl -, Br -, I -, carboxylate radical, sulfonate radical negative ion; (A) and (B) ionic liquid of structural formula can be 1-(diphenylphosphino) ethyl-3-Methylimidazole bromine salt, 1-(diphenylphosphino) ethyl-3-methyl imidazolium tetrafluoroborate, 1-(diphenylphosphino) butyl-3-Methylimidazole bromine salt, 1-(diphenylphosphino) butyl-3-ethyl imidazol(e) hexafluoro phosphonate, 1-butyl-2-(diphenylphosphino)-3-Methylimidazole bromine salt, 1-butyl-2-(diphenylphosphino)-3-methyl imidazolium tetrafluoroborate, 1-butyl-2-(diphenylphosphino)-3-Methylimidazole hexafluoro phosphonate ionic liquid.
2. (A) and (B) the imidazole ion liquid type organophosphorus ligand of structural formula can be by obtaining metal complex catalyst with the metal of the 8th, 9 and 10 families or the combination of its compound in the claim 1; Metal complex catalyst is ML nX mForm, wherein M is the 8th, 9 or 10 family's metals, preferable alloy Pd, Ru, Rh and Pt, more preferably Pd and Rh, L is the ion liquid type organophosphorus ligand, X is halogen, carbonate, bicarbonate radical, nitrate radical, carboxylate radical or sulfonate radical, and n is the numerical value that is equal to or less than the metal-complexing number, and m is 1 or 2 and equal the oxidation state of metal.
3. the metal complex catalyst in the claim 2 can make alkene and CO and alcohols generation hydroesterification reaction generate the corresponding carboxylic acid ester in the presence of imidazole ion liquid type organophosphorus ligand and acid source; Acid source can be one or more pKa that measure in dilute aqueous soln less than 5 acid.
4. method according to claim 3, hydroesterification reaction carries out under 20～150 ℃ temperature, preferably reacts under 60～100 ℃ temperature; Pressure is 0.1～100MPa, preferred 1～10MPa.
CN 201010194349 2010-05-28 2010-05-28 Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification Pending CN101857608A (en)

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Cited By (8)

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CN102658205A (en) * 2012-04-19 2012-09-12 华东师范大学 Catalyst for producing aldehyde through hydroformylation of alkene and application thereof
CN102952099A (en) * 2011-08-30 2013-03-06 海洋王照明科技股份有限公司 Pyrrole ionic liquid, and preparation method and application thereof
CN103435649A (en) * 2013-07-31 2013-12-11 宁波大学 Bidentate phosphine functionalization ionic liquid and synthetic method thereof
US10544174B2 (en) 2016-07-19 2020-01-28 Evonik Degussa Gmbh Process for the alkoxycarbonylation of ethylenically unsaturated compounds with monophosphine ligands
CN112939776A (en) * 2021-02-02 2021-06-11 中国科学院过程工程研究所 Method for reinforcing long-chain olefin hydrogen esterification reaction by ionic liquid
CN114181149A (en) * 2021-12-30 2022-03-15 浙江本立科技股份有限公司 Synthetic method of 3, 4-dimethylpyrazole
CN114308129A (en) * 2021-11-24 2022-04-12 中国科学院兰州化学物理研究所 Catalyst composition for olefin alkoxycarbonylation and preparation method and application thereof
CN114849786A (en) * 2021-02-04 2022-08-05 中国科学院过程工程研究所 Imidazole sulfonic acid ionic liquid based palladium-phosphine complex catalyst for synthesizing methyl propionate by ethylene methyl hydrogen esterification

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Cited By (13)

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CN102952099A (en) * 2011-08-30 2013-03-06 海洋王照明科技股份有限公司 Pyrrole ionic liquid, and preparation method and application thereof
CN102952099B (en) * 2011-08-30 2015-05-06 海洋王照明科技股份有限公司 Pyrrole ionic liquid, and preparation method and application thereof
CN102658205A (en) * 2012-04-19 2012-09-12 华东师范大学 Catalyst for producing aldehyde through hydroformylation of alkene and application thereof
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
CN103435649A (en) * 2013-07-31 2013-12-11 宁波大学 Bidentate phosphine functionalization ionic liquid and synthetic method thereof
CN103435649B (en) * 2013-07-31 2015-12-02 宁波大学 A kind of Bidentate phosphine functionalization ionic liquid and synthetic method thereof
US10544174B2 (en) 2016-07-19 2020-01-28 Evonik Degussa Gmbh Process for the alkoxycarbonylation of ethylenically unsaturated compounds with monophosphine ligands
CN112939776A (en) * 2021-02-02 2021-06-11 中国科学院过程工程研究所 Method for reinforcing long-chain olefin hydrogen esterification reaction by ionic liquid
CN114849786A (en) * 2021-02-04 2022-08-05 中国科学院过程工程研究所 Imidazole sulfonic acid ionic liquid based palladium-phosphine complex catalyst for synthesizing methyl propionate by ethylene methyl hydrogen esterification
CN114849786B (en) * 2021-02-04 2023-09-05 中国科学院过程工程研究所 Imidazole sulfonic acid ionic liquid-based palladium phosphine complex catalyst for synthesizing methyl propionate through ethylene hydro-methyl esterification
CN114308129A (en) * 2021-11-24 2022-04-12 中国科学院兰州化学物理研究所 Catalyst composition for olefin alkoxycarbonylation and preparation method and application thereof
CN114181149A (en) * 2021-12-30 2022-03-15 浙江本立科技股份有限公司 Synthetic method of 3, 4-dimethylpyrazole
CN114181149B (en) * 2021-12-30 2024-04-02 浙江本立科技股份有限公司 Synthesis method of 3, 4-dimethylpyrazole

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