CN101768045B - Method for preparing halogenated hydrocarbons from strong acidic ionic liquid - Google Patents

Method for preparing halogenated hydrocarbons from strong acidic ionic liquid Download PDF

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CN101768045B
CN101768045B CN2010100301481A CN201010030148A CN101768045B CN 101768045 B CN101768045 B CN 101768045B CN 2010100301481 A CN2010100301481 A CN 2010100301481A CN 201010030148 A CN201010030148 A CN 201010030148A CN 101768045 B CN101768045 B CN 101768045B
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rmim
ionic liquid
hso
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methylimidazole
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CN101768045A (en
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李华
朱江
章亚东
胡国勤
赵蕾
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Zhengzhou University
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Abstract

The invention discloses a new method for preparing halogenated hydrocarbons, which belongs to the technical field of fine chemical synthesis. In the method, strong acidic ionic liquid is used as a halogenated agent, a catalyst and a solvent and reacts for 30 to 120 minutes at the temperature of between 60 and 100 DEG C to generate the halogenated hydrocarbons. Compared with the current methods, the method has the advantages of green preparation process, high product yield, short technological flow, mild reaction conditions, simple process, easy isolation of the product from the ionic liquid, easy recovery of the ionic liquid from a reaction system, recycling and the like, is favorable for saving energy resources, lowering investment, reducing environmental pollution and the like, and has a good application prospect.

Description

Method for preparing halogenated hydrocarbons from strong acidic ionic liquid
Technical field
The invention belongs to the catalyst preparation technical field, relate to the halogenated hydrocarbon compound synthetic method, relate in particular to the preparation method of long carbochain class halohydrocarbon in the preparation of strongly-acid ionic liquid.
Background technology
At present, alcoholic extract hydroxyl group displacement synthesizing halohydrocarbon mainly adopts following several method:
One. use the sulfur oxychloride method
Figure G2010100301481D00011
The halo product space configuration that Zhang Zhuyong [Minute Organic Synthesis unit process M. Shanghai: press of East China University of Science, 2003.] adopts this method to obtain can keep, and owing to only generating product and sulfurous gas after reaction, so product classification is easy to.But sulfur oxychloride character is very active, and is unstable, usually only is used for the chlorination of alcoholic extract hydroxyl group.
Two. with three halogenation phosphine preparations
Figure G2010100301481D00012
He Jiuling [Advanced Organic Chemistry M. Beijing: Chemical Industry Press, 1987.] adopts this method to synthesize hydrobromic ether, and reaction is easily controlled, and product yield is also higher.But three halogenation phosphines are volatile, and toxicity is large, and post-reaction treatment is also more loaded down with trivial details.
Three. with halogen (Br, I) and red phosphorus preparation
Figure G2010100301481D00013
Vogel Arthur[Textbook of Practical Organic Chemistry, 4 thEd.London:Longman Group Limited, 1978,391] adopt this method to synthesize hydrobromic ether, this method has avoided three halogenation phosphines volatile, the characteristics that toxicity is large.But reaction process is very violent, is difficult to control, and aftertreatment is loaded down with trivial details, and the purifying of product is difficulty comparatively.
Four. with the preparation of triphenylphosphine halogen
Figure G2010100301481D00021
P.J.Garegg[J.Chem.Soc.Perkin Trans.1,1980 (12), 2866-2869] adopt this method that a kind of new iodine substitution reaction is provided, reaction conditions is also gentleer, but technique is comparatively complicated, first obtain 2,4,5-, three iodo imidazoles with a large amount of iodine and imidazoles reaction, react with it and pure and mild triphenylphosphine again, obtain the iodate product, product separation is very difficult, and other reagent also are difficult to separate and recycle.
Five. prepare with haloid acid
Figure G2010100301481D00022
Vogel Arthur[Textbook of Practical Organic Chemi stry, 4 thEd.London:Longman Group Limited, 1978,384] adopt this method to synthesize halohydrocarbon, this method technological process is simple, and product also is easier to separate.But simple only use haloid acid, the yield of product is lower, usually adds the vitriol oil to make catalyzer, improves product yield, simultaneously because strong acidic condition has brought heavy corrosion to equipment, and a large amount of waste water of generation after reaction, environment is caused very large pollution.
Six. with the preparation of sodium halide (potassium) sulphate method
Kamm, O.; Marvel, C.S.[Organic Syntheses, 1921,1,3] adopt this method to synthesize hydrobromic ether, this method can be avoided the haloid acid that uses volatility and corrodibility very strong, but it need to be with the relatively large vitriol oil, and product yield does not have aforesaid method five height.A large amount of solid waste and waste liquid have caused very large pollution to environment equally.
Seven. prepare with tetrahalide
Figure G2010100301481D00031
R.Appel[Angewandte Chemie, 1975,87 (24), 863-874] adopt this method to synthesize hydrobromic ether, this method reaction conditions is gentle, and speed of reaction is also very fast.But need to use the larger benzene of toxicity as solvent, reaction needs to consume tri octyl phosphine and obtains trioctyl phosphine oxide, and not easily separated with product.
Eight. prepare with acetyl halide
Luciano Barboni[J.Med.Chem., 2001,44 (10), 1576-1587] adopt this method to synthesize hydrobromic ether, this method need to operate at-15 ℃ of temperature, severe reaction conditions.Product yield is relatively low.
Nine. with trialkyl phosphite and haloalkane reaction
Figure G2010100301481D00033
A.E.Arbuzov[J.Russ.Phys.Chem.Soc., 1906,38,687] adopt this method to synthesize halohydrocarbon, i.e. famous Arbuzov reaction.But the reaction raw materials trialkyl phosphite is not easy to obtain.
Ten. with dialkylimidazolium halogenide [Rmim] X preparation
Rex X.Ren[Org.1ett., 2001,3 (23) 3727-3728] adopt ionic liquid as halogenating agent, make catalyzer with traditional organic acid or mineral acid, although reaction conditions is gentle, long reaction time, yield are also unstable.
11. with imidazoles halide salt [Himn] X preparation
Tang Jie, the people such as Sun Jing adopt acid type ionic liquid [Hmim] +X -(X=Cl, Br, I) in, primary alconol or hexalin change into the method [CN:1440958A of haloalkane, 2003.9.10] the preparation halohydrocarbon, the ionic liquid advantage with conspicuous characteristics of this method, after reaction, ionic liquid can recycle, but it directly obtains ionic liquid [Hmim] X with imidazoles and haloid acid neutralization, its strength of acid is very low, make alcoholic extract hydroxyl group protonated very difficult, therefore when doing halogenating reaction with this type of ionic liquid, its temperature of reaction is high, long reaction time, and product yield is also lower.
Summary of the invention
The object of the invention is to provide a kind of preparation technology green, widely applicable, reaction conditions is gentle, reactive behavior is high, selectivity is better, product is easy to separate from reaction system, reacted ionic liquid or inner salt are easy to reclaim and can be recycled, and be energy-saving and cost-reducing, the halohydrocarbon novel preparation method of organic solvent-free discharging in reaction process.
The present invention adopts following two kinds of technical schemes to realize above-mentioned purpose:
Method one: (1) adds 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO in reaction system 3Rmim] X, alcohol, organic solvent-free, 60～100 ℃, reacted 30～120 minutes, generate the target product halohydrocarbon; And backward reaction solution adds a certain amount of deionized water, with solvent extraction reaction solution, organic phase and the water layering of lower boiling nonpolar or low-pole.Revolve after the organic phase washing and drying and steam solvent, obtain target product; (2) then add haloid acid to aqueous phase, stir, react, evaporation is anhydrated, and obtains 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] X, recycle; 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] the X consumption is 1～1.5 times of hydroxyl mole number in alcohols material; X is Cl, Br, I; R is alkyl, preferred propyl group, butyl.Described alcohol is that the C atomicity is 6～12 monobasic or polynary primary alconol.
1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] technological process that recycles of X is as follows:
Figure G2010100301481D00051
1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] double halogenating agent, the catalysts and solvents done of X ionic liquid.Its preparation method is as follows:
Figure G2010100301481D00052
With 1, ω-alkylsulphonic acid lactone is dissolved in a certain amount of methyl alcohol, in ethanol or acetone, drips the solution of N-Methylimidazole under room temperature, stirring at room reaction 24 hours, obtain clear crystal, after desolventizing, use deionized water dissolving, drip again a certain amount of haloid acid, after acidifying 3 hours, evaporation dewaters, and obtains 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] X.Wherein, n is the number of carbon atom in 1, ω-alkyl base sultones; X is Cl, Br, I.
Method two: (1) adds ionic liquid dialkylimidazolium halogenide [Rmim] X, alcohol, strongly-acid ionic liquid 1-alkyl-3-Methylimidazole hydrosulfate [Rmim] HSO in reaction system 4, organic solvent-free in 60～100 ℃ of reactions 30～120 minutes, generates the target product halohydrocarbon; And backward reaction solution adds a certain amount of deionized water, with solvent extraction reaction solution, organic phase and the water layering of lower boiling nonpolar or low-pole.Revolve after the organic phase washing and drying and steam solvent, obtain target product; (2) then add sodium halide or potassium halide to stir at aqueous phase, evaporation is anhydrated, add methyl alcohol or ethanol to stir, react at its residue, remove by filter sodium sulfate and unreacted sodium halide or the potassium halide of generation, will obtain dialkylimidazolium halogenide [Rmim] X and recycle; Dialkylimidazolium halogenide [Rmim] X and strongly-acid ionic liquid [Rmim] HSO 4Consumption is respectively 1～1.5 times of hydroxyl mole number in alcohols material; X is Cl, Br, I; The preferred ethyl of R, propyl group, sec.-propyl, butyl.Described alcohol is that the C atomicity is 6～12 monobasic or polynary primary alconol.
The present invention adopts composition and the content of GC9800 gas chromatographic analysis product, and analytical conditions for gas chromatography used is as follows:
Post case temperature: 170 ℃; Press before post: 0.043MPa;
Vaporization temperature: 270 ℃; Hydrogen pressure: 0.025MPa;
Detected temperatures: 270 ℃; Air pressure: 0.03MPa;
Instrument decay: 1/1; Detector: FID;
Sample: ALDRICH halohydrocarbon standard substance (AR level); Sensitivity: 2;
Sample size: 0.2 μ L; Tail blows: 0.04MPa;
Carrier gas kind: N 2Chromatographic column: SE-54 30m * 0.53mm;
N 2Flow velocity: 40mL/min; H 2Flow velocity: 20mL/min;
Advantage of the present invention: 1, in the reaction with ionic liquid dialkylimidazolium halogenide [Rmim] X and strong Bronsted acidic ion liquid [Rmim] HSO 4Be halogenating agent, catalysts and solvents, reacted ionic liquid can by carrying out regenerating after ion-exchange in alcoholic solvent with sodium halide (potassium), recycle.
2,1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO in the reaction 3Rmim] the X ionic liquid doubles as halogenating agent, and catalysts and solvents after adding haloid acid after reaction, can be recycled.
3, technological process is green, and reaction conditions is gentle, and speed of reaction is fast, and product yield high (the chlorination yield is greater than 80%, and bromo and iodide reaction yield are greater than 90%) separates easyly, save energy and reduce the cost, and ionic liquid can be recycled.
Embodiment
For the present invention will be described better, enumerate embodiment as follows:
Embodiment one
In reaction system, add 1,7-heptanediol 0.2mol, 1-ethyl 3-Methylimidazole bromine [emim] Br 0.5mol, 1-ethyl-3-methylimidazole hydrosulfate [emim] HSO 40.5mol, 60～100 ℃ of temperature of reaction, reaction 60min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, organic phase is through washing and drying, revolves to steam solvent, obtains product 1,7-dibromo-heptane, product yield are 93%.Water adds the Sodium Bromide of 0.5mol, after stirring, removes moisture, adds methyl alcohol to carry out ion-exchange, reacts 24 hours, filters out unreacted Sodium Bromide and sodium sulfate, revolve evaporate solvent after, the ionic liquid that obtains [emim] Br recycles.
Embodiment two
In reaction system, add n-Octanol 0.1mol, 1-propyl group 3-Methylimidazole chlorine [pmim] Cl 0.1mol, 1-propyl group-3-Methylimidazole hydrosulfate [pmim] HSO 40.1mol, 60～100 ℃ of temperature of reaction, reaction 120min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, the organic phase washing and drying revolves and steams solvent, obtains 1-chloro-octane, product yield is 82%.Water adds the sodium-chlor of 0.2mol, and other is with example 1.
Embodiment three
In reaction system, add 1,7-heptanediol 0.2mol, 1-sec.-propyl 3-Methylimidazole iodine [ipmim] I 0.4mol, 1-sec.-propyl-3-Methylimidazole hydrosulfate [ipmim] HSO 40.4mol, pass into nitrogen protection, 60～100 ℃ of temperature of reaction, reaction 30min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, the organic phase washing and drying revolves and steams solvent, obtains 1,7-diiodo-heptane, product yield is 90%.Water adds the sodium iodide of 0.5mol, and other are with embodiment 1.
Embodiment four
In reaction system, add 1,7-heptanediol 0.2mol, 1-(3-sulfonic group) propyl group-3-Methylimidazole bromine salt [HSO 3Pmim] Br 0.5mol, 60～100 ℃ of temperature of reaction, reaction 60min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, the organic phase washing and drying revolves and steams solvent, obtains 1,7-dibromo-heptane, product yield is 95%.Water adds the Hydrogen bromide of 0.4mol, and acidifying 3 hours obtains [HSO except after anhydrating 3Pmim] Br, recycle.
1-(3-sulfonic group) propyl group-3-Methylimidazole bromine salt [HSO 3Pmim] the Br preparation: with 1,3-propyl sulfonic acid lactone is dissolved in methyl alcohol, in ethanol or acetone, drips the solution of N-Methylimidazole under room temperature, stirring at room reaction 24 hours, obtain clear crystal, after desolventizing, use deionized water dissolving, drip again Hydrogen bromide, after acidifying 3 hours, evaporation dewaters, and obtains 1-(3-sulfonic group) propyl group-3-Methylimidazole bromine salt [HSO 3Pmim] Br.
Embodiment five
In reaction system, add n-Octanol 0.1mol, 1-(4-sulfonic group) butyl-3-Methylimidazole villaumite [HSO 3Bmim] Cl 0.12mol, 60～100 ℃ of temperature of reaction, reaction 120min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, the organic phase washing and drying revolves and steams solvent, obtains 1-chloro-octane, product yield is 86%.Water adds the hydrochloric acid of 0.12mol, and acidifying 3 hours obtains [HSO except after anhydrating 3Bmin] Cl, recycle.
1-(4-sulfonic group) butyl-preparation method is the same for 3-Methylimidazole villaumite.
Embodiment six
In reaction system, add 1,7-heptanediol 0.2mol, 1-(3-sulfonic group) propyl group-3-Methylimidazole salt compounded of iodine [HSO 3Pmim] I 0.4mol, logical nitrogen protection, 60～100 ℃ of temperature of reaction, reaction 30min, react complete after, add a certain amount of water, use hexanaphthene extractive reaction liquid, the organic phase washing and drying revolves and steams solvent, obtains 1,7-diiodo-heptane, product yield is 92%.Water adds 0.22mol sodium iodide and hydrochloric acid, and acidifying 3 hours except after anhydrating, with the methylene dichloride dissolving, obtains [HSO after removing methylene dichloride 3Pmim] I, recycle.
The method process is green, and reactive behavior is high, and ionic liquid can be recycled, to save energy, reduce investment, environmental contamination reduction is very favourable, is the effective way that realizes suitability for industrialized production.

Claims (2)

1. method for preparing halogenated hydrocarbons from strong acidic ionic liquid, is characterized in that, realize as follows: (1) adds 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO in reaction system 3Rmim] X, alcohol, organic solvent-free, 60～100 ℃, reacted 30～120 minutes, generate the target product halohydrocarbon; And backward reaction solution adds deionized water, extractive reaction liquid, organic phase and water layering; Revolve after the organic phase washing and drying and steam solvent, obtain target product; (2) then add haloid acid to aqueous phase, stir, react, evaporation is anhydrated, and obtains 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] X, recycle; 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmin] the X consumption is 1～1.5 times of hydroxyl mole number in alcohols material; Described 1-(omega-sulfonic base) alkyl-3-Methylimidazole halogen [HSO 3Rmim] X wherein X be Cl, Br, I; R is propyl group, butyl; Described alcohol is that the C atomicity is 6～12 monobasic or polynary primary alconol.
2. method for preparing halogenated hydrocarbons from strong acidic ionic liquid, it is characterized in that, realize as follows: (1) adds ionic liquid dialkylimidazolium halogenide [Rmim] X, alcohol, strongly-acid ionic liquid 1-alkyl-3-Methylimidazole hydrosulfate [Rmim] HSO in reaction system 4, organic solvent-free in 60～100 ℃ of reactions 30～120 minutes, generates the target product halohydrocarbon; And backward reaction solution adds deionized water, extractive reaction liquid, organic phase and water layering; Revolve after the organic phase washing and drying and steam solvent, obtain target product; (2) then add sodium halide or potassium halide to stir at aqueous phase, evaporation is anhydrated, add methyl alcohol or ethanol to stir, react at its residue, remove by filter sodium sulfate and unreacted sodium halide or the potassium halide of generation, obtain dialkylimidazolium halogenide [Rmim] X and recycle; Dialkylimidazolium halogenide [Rmim] X and strongly-acid ionic liquid [Rmim] HSO 4Consumption is respectively 1～1.5 times of hydroxyl mole number in alcohols material; Described dialkylimidazolium halogenide [Rmim] X wherein X is Cl, Br, I; The R of described dialkylimidazolium halogenide [Rmim] X is ethyl, propyl group; Described strongly-acid ionic liquid [Rmim] HSO 4R be ethyl, propyl group, butyl; Described alcohol is that the C atomicity is 6～12 monobasic or polynary primary alconol.
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CN104672053B (en) * 2013-11-29 2016-08-24 上虞新和成生物化工有限公司 Ionic liquid application in the preparation of bromoethane
CN106365951B (en) * 2016-08-31 2018-12-11 濮阳天源生物科技有限公司 Prepare the recycling technique of 2- N-Propyl Bromide during 2,2- diisopropyl propionitrile
CN113896614B (en) * 2021-11-08 2024-04-02 山东绿色海洋化工研究院有限公司 Method for continuously synthesizing chlorobutane in non-aqueous system

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