CN103232396B - Three selective ionic liquids and synthesizing method thereof - Google Patents
Three selective ionic liquids and synthesizing method thereof Download PDFInfo
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- CN103232396B CN103232396B CN201310134353.6A CN201310134353A CN103232396B CN 103232396 B CN103232396 B CN 103232396B CN 201310134353 A CN201310134353 A CN 201310134353A CN 103232396 B CN103232396 B CN 103232396B
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Abstract
The invention relates to selective ionic liquids and a synthesizing method. The invention belongs to the technical field of ionic liquid. The ionic liquids are 1-ethyl-3-methylimidazole bistrifluoromethyl sulfonylimide salt, 1-n-propyl acetate-3-methylimidazole bistrifluoromethyl sulfonylimide salt, and 1-p-methyl ethyl benzoate-3-methylimidazole bistrifluoromethyl sulfonylimide salt. The preparation method comprises the steps that: under the protection of N2, N-methylimidazole and halogenated hydrocarbon with a molar ratio of 1:1-1.5 are added into a reaction container, and acetonitrile is added; refluxing is carried out for 12h under a temperature of 55 DEG C; separation is carried out, such that a halogen ionic liquid crude product is obtained; the product is washed by using ethyl acetate and is dried, such that purified halogen ionic liquid is obtained; a water solution of bistrifluoromethyl sulfonylimide lithium salt is added into the ionic liquid, and stirring is carried out under room temperature; lower-layer ionic liquid is washed several times by using distilled water; and drying is carried out, such that a finished product is obtained. The preparation process is simple and controllable, and the entire reaction process is stable. The method has potential to be used in industrial productions.
Description
Technical field
The present invention relates to three kinds of synthetic methods based on the selectively novel imidazole class ionic liquid of SVOCs in room air, particularly relate to N-Methylimidazole and with the halogenated hydrocarbon derivatives of particular functional group for raw material, synthesize three kind 1,3-bis-glyoxaline cations and NTf replaced
2for the new selective ionic liquid of negatively charged ion, object measures for the extracting and enriching of contaminant trace species SVOCs in room air and follow-up Instrument crosslinking, belongs to Ionic liquids technologies field.
Background technology
Half volatile organic contaminant (SVOCs) refers to the organic compound of boiling point within the scope of 240 ~ 400 DEG C, although saturation vapour pressure is lower, but adsorptivity is very strong, compared with VOCs, SVOCs is more stable in the environment, not easily degrades, and can there is several years or longer time in indoor environment, persistent organism pollutent (persistent organic pollutants, POPs) in this characteristic and atmospheric environment has obvious similarity.SVOCs mainly comprises fire retardant polychlorobiphenyl, Polybrominated biphenyl, Poly Brominated Diphenyl Ethers; Softening agent; Organic insecticide; Polycyclic aromatic hydrocarbons (PAHs); Duo chlorodiphenyl Bing dioxin (PCDDs), polychlorinated dibenzo (PCDFs) etc.Wherein polycyclic aromatic hydrocarbons (PAHs) is strong carcinogen, according to estimates the annual patient about 260,000 being diagnosed as cancer because of contact polycyclic aromatic hydrocarbons.The team of domestic and international co-worker's composition is studied through the experiment nosetiology of 22 years and population epidemiology in Yunnan, " Science " reports this discovery, i.e. the increasing obviously to raise with lung cancer morbidity rate and there is significant correlation of indoor benzo (a) pyrene concentration.The international Important Academic periodical report such as " EnvironmentalHealth Perspectives ", main plasticizer phthalic acid ester can make children produce allergic symptom, cause endocrine disturbance and young girl's breast development precocity, the growth affecting male reproductive system even causes reproductive system deformity and metabolic dysfunction etc., serious harm HUMAN HEALTH.Research finds that fire retardant such as Polybrominated biphenyl (PBBs) and polychlorobiphenyl (PCBs) can endanger neural system, immunity system, liver, kidney, suppresses Triiodothyronine, also may cause human cancer; Poly Brominated Diphenyl Ethers (PBDEs) can damage study and the motor capacity of rodent (large and small mouse), and cause hepatotoxicity, endocrine disturbance even produces genotoxicity.Epidemiology and toxicologic study have confirmed that half volatile organic contaminant (SVOCs) can produce great disadvantageous effect to HUMAN HEALTH really, human reproductive system, respiratory system and endocrine system can be injured, infringement DNA, not only endanger we in present age but also affect offspring and this harm is long-range generation-inter-, therefore selective enrichment separation carried out to half volatile organic contaminant in indoor environment (SVOCs) and measure significant.
Ionic liquid at room temperature (Room temperature ionic liquids, write a Chinese character in simplified form: RTILS), refer to the ionic compound be in a liquid state in room temperature or near room temperature temperature (<100 DEG C) be made up of organic cation and inorganic anion or organic anion.Since Wilkes in 1992 reports the stable a tetrafluoro borate glyoxaline ion liquid of first relative water and air, ionic liquid obtains fast development.Compare with supercutical fluid etc. with traditional organic solvent, water, ionic liquid has following outstanding advantages: (1) wider liquid temperature scope, and the most <100 DEG C of its fusing point, even can be low to moderate-90 DEG C; (2) extremely low vapour pressure, non-volatility, non-combustible; (3) good solubility, can dissolved organic matter, inorganics, organometallic compound and superpolymer etc., seldom solvation and solvolysis phenomenon occurs; (4) good chemical stability and thermostability; (5) good electroconductibility and wider electrochemical stability electrochemical window; (6) have designability, by selecting the functional group that suitable anions and canons combines or grafting is suitable, can regulate the character of ionic liquid, design the ionic liquid with various function, be therefore otherwise known as " can design solvent ".The peculiar property that ionic liquid has makes it be subject to extensive concern in fields such as electrochemistry, catalysis, separation, organic synthesis, functional materials and friction, lubrications.This is not only traditional chemical reaction and provides transformation space, also for the development of Green Chemistry opens new field, to have breakthrough for solving the problem of environmental pollution that in modern chemical industry, conventional organic solvents is brought, be a kind of programmable desirable green organic solvent.
Ionic liquid development rapidly, successively experienced by the first-generation ionic liquid-chloroaluminate ionic liquid to water and air instability, the third generation ionic liquid of the s-generation ionic liquid that resistant to hydrolysis, stability are strong and functionalization.Ionic liquid is of a great variety, but up to the present most study, most widely used general, technology more ripe be glyoxaline ion liquid.
What in document, report synthesis was more is the glyoxaline ion liquid that alkane replaces, we according to the actual demand of oneself for the SVOCs design and synthesis in room air new selective glyoxaline ion liquid, namely new particular functional group is introduced by changing cationic branched-chain structure, make it can meet certain particular demands to improve ionic liquid physicochemical property, show ionic liquid purposes specificity, specific aim further.
Summary of the invention
The object of the invention is the preparation method that three kinds of new selective glyoxaline ion liquids are provided for half volatile organic contaminant in room air (SVOCs), and the conditions favouring of gentleness is in the realization of large-scale production.This synthesis is with N-Methylimidazole, halogenated hydrocarbon derivative for reaction starting raw material, and obtain through quaternary ammoniated, ion-exchange two-step reaction, the negatively charged ion of end product is NTf
2 -.The structural formula of selectivity glyoxaline ion liquid provided by the invention is:
Its preparation process is: at N
2under protection, solvent acetonitrile and N-Methylimidazole is added in reaction vessel, N-Methylimidazole and halogenated hydrocarbon derivatives ethyl bromoacetate or acetic acid n-propyl bromide or 4-bromomethyl-benzoic acid ethyl ester are joined in reaction vessel by mol ratio 1:1 ~ 1.5, constantly be stirred to after mixing under room temperature, be warming up to 55 DEG C of back flow reaction 12h, reacting complete system is divided into two-layer, what lower floor obtained is halogen ionic liquid crude product, upper strata is reaction solvent and excessive unreacted reaction raw materials, separation obtains halogen ionic liquid crude product, with ethyl acetate washing crude product several, underpressure distillation is except desolventizing and ethyl acetate, namely vacuum-drying obtain the ionic liquid intermediate after purifying, with water as solvent, continue at N
2under protection, in ionic liquid intermediate, add bis trifluoromethyl sulfimide lithium (LiNTf
2) aqueous solution, ionic liquid intermediate and bis trifluoromethyl sulfimide lithium (LiNTf
2) mol ratio be 1:(1 ~ 1.5) (preferred 1:(1 ~ 1.20)), stirring at room temperature 12h, reaction terminates rear solution and divides two-layer, discard upper strata aqueous phase, with distilled water wash lower floor ionic liquid repeatedly, until water layer is in neutral, remove excessive moisture, vacuum-drying obtains bis trifluoromethyl sulfimide ionic liquid end product.
The mol ratio of N-Methylimidazole and halogenated hydrocarbon derivatives is 1:1 ~ 1:1.5, and reaction process will constantly stir, and control temperature ensures backflow, to ensure higher reaction yield.Solvent in reaction process is by underpressure distillation, and recoverable, save energy, reduces costs.With water as solvent, environment friendly and pollution-free, simple to operate, aftertreatment is easy.This preparation process simply can manipulate, and whole reaction process is stablized, and can consider to be applied to suitability for industrialized production.
Ionic liquid preparation method provided by the present invention, because having the advantages such as device is simple, easy handling, reaction conditions are less demanding, can consider the realization of large-scale production.Protect with the interference avoiding oxygen and water vapour in air with N2 in the synthetic method of ionic liquid of the present invention, effectively improve reaction yield.Adding appropriate solvent is ensure that speed of reaction can not be influenced because generating the larger product of viscosity, and suitable mol ratio contributes to the unmanageable reactant of high boiling point and carries out completely, simplifies subsequent purification process.Underpressure distillation removal of impurities can be recycled simultaneously, has not only reduced the wasting of resources but also protection of the environment.
Embodiment
At N
2under protection; add solvent acetonitrile; N-Methylimidazole and halogenated hydrocarbon derivatives is added in reaction vessel; its mol ratio is made to be 1:1 ~ 1.5; constantly stirring under room temperature before this reheats to 55 DEG C of back flow reaction 12h, is separated and obtains bromo imidazole ion liquid crude product, with ethyl acetate washing crude product several; underpressure distillation is except desolventizing and ethyl acetate, and namely vacuum-drying obtain the bromo ionic liquid intermediate product after preliminary purification.With appropriate distilled water dissolve respectively bis trifluoromethyl sulfimide lithium and above gained purify after intermediate product, be 1:1 ~ 1.2 by its mol ratio of both mixture control, stirring at room temperature 12h, solution divides two-layer, discard upper strata aqueous phase, with distilled water wash lower floor ionic liquid repeatedly, until water layer is in neutral, remove excessive moisture, namely vacuum-drying obtain bis trifluoromethyl sulfimide ionic liquid end product.
Embodiment 1
1-ethyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt ([CH
2cOOCH
2cH
3mIM] NTf
2)
At N
2under protection, with 20ml acetonitrile as solvents, N-Methylimidazole 2.4mL (0.03mol) is added in reaction vessel, 3.7mL (0.033mol) ethyl bromoacetate is slowly dripped in reaction vessel, itself and ethyl bromoacetate mol ratio is made to be 1:1 ~ 1.5, constantly stirred under room temperature before this and made both fully mixing, DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus is used to be heated to 55 DEG C of back flow reaction 12h, obtain bromo 1-ethyl acetate base-3-Methylimidazole ionic liquid crude product, after its cooling, with ethyl acetate washing crude product several, underpressure distillation is except desolventizing and ethyl acetate, namely vacuum-drying obtain the ionic liquid intermediate product 1-ethyl acetate base-3-Methylimidazole bromine salt after purifying.With appropriate distilled water dissolve respectively bis trifluoromethyl sulfimide lithium and above gained purify after 1-ethyl acetate base-3-Methylimidazole bromine salt, be 1:1 ~ 1.2 by its mol ratio of both mixture control, stirring at room temperature 12h, leave standstill, solution divides two-layer, discards upper strata aqueous phase, with distilled water wash lower floor ionic liquid repeatedly, until water layer is in neutral, remove excessive moisture, namely vacuum-drying obtain ionic liquid end product 1-ethyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt.
Embodiment 2
1-n-propyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt ([CH
2cOOCH
2cH
2cH
3mIM] NTf
2)
At N
2under protection, with 20ml acetonitrile as solvents, N-Methylimidazole 2.4mL (0.03mol) is added in reaction vessel, 4.3mL (0.033mol) acetic acid n-propyl bromide is slowly dripped in reaction vessel, itself and acetic acid n-propyl bromide mol ratio is made to be 1:1 ~ 1.5, constantly stirred under room temperature before this and made both fully mixing, DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus is used to be heated to 55 DEG C of back flow reaction 12h, obtain bromo 1-n-propyl acetate base-3-Methylimidazole ionic liquid crude product, after its cooling, with ethyl acetate washing crude product several, underpressure distillation is except desolventizing and ethyl acetate, namely vacuum-drying obtain the ionic liquid intermediate product 1-n-propyl acetate base-3-Methylimidazole bromine salt after purifying.With appropriate distilled water dissolve respectively bis trifluoromethyl sulfimide lithium and above gained purify after 1-n-propyl acetate base-3-Methylimidazole bromine salt, be 1:1 ~ 1.2 by its mol ratio of both mixture control, stirring at room temperature 12h, leave standstill, solution divides two-layer, discards upper strata aqueous phase, with distilled water wash lower floor ionic liquid repeatedly, until water layer is in neutral, remove excessive moisture, namely vacuum-drying obtain ionic liquid end product 1-n-propyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt.
Embodiment 3
1-ethyl p-methyl benzoate base-3-Methylimidazole bis trifluoromethyl sulfimide salt ([CH
2c
6h
4cOOCH
2cH
3mIM] NTf
2)
At N
2under protection, with 25ml acetonitrile as solvents, add bromomethyl-benzoic acid ethyl ester 8.0g (0.033mol) in reaction vessel, 2.4mL (0.03mol) N-Methylimidazole is slowly dripped in reaction vessel, constantly stirred under room temperature before this and made both fully mixing, DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus is used to be heated to 55 DEG C of back flow reaction 12h, react complete and treat that it cools, with ethyl acetate washing several, underpressure distillation is except desolventizing and ethyl acetate, namely vacuum-drying obtain the ionic liquid intermediate product 1-ethyl p-methyl benzoate base-3-Methylimidazole bromine salt after purifying.With appropriate distilled water dissolve respectively bis trifluoromethyl sulfimide lithium and above gained purify after 1-ethyl p-methyl benzoate base-3-Methylimidazole bromine salt, be 1:1 ~ 1.2 by its mol ratio of both mixture control, stirring at room temperature 12h, leave standstill, solution divides two-layer, discard upper strata aqueous phase, with distilled water wash lower floor ionic liquid repeatedly, until water layer is in neutral, remove excessive moisture, namely vacuum-drying obtain ionic liquid end product 1-ethyl p-methyl benzoate base-3-Methylimidazole bis trifluoromethyl sulfimide salt.
Product structure is identified
[CH
2COOCH
2CH
3MIM]NTf
2
IR,ν/cm
-1:3164、3128（ν(im-CH)），2992、2915（ν
as(CH
3)/ν
as(CH
2)），1753（ν(-C=O)），1570（ν(C=N)/ν(C=C)），1471、1439（δ(CH
2)/δ
as(CH
3)），1351（ν(S=O)），1194（ν(C-F)），1138（δ(S=O)），1057（δ(C-F)）。
1HNMR（400MHZ:DMSO-d6;δ/ppm relative to TMS）
9.063（1H,s,NCHN），7.721（2H,s,NCH），5.231（2H,s,NCH2），4.212（2H,q,J=7.2HZ,-OCH2），3.907（3H,s,NCH3），1.245（3H,t,J=7.2HZ,-OCH2CH3），MS:m/z169.10(M
+)，279.92（NTf
2 -）
[CH
2COOCH
2CH
2CH
3MIM]NTf
2
IR,ν/cm
-1:3163、3127（ν(im-CH)），2974、2886（ν
as(CH
3)/ν
as(CH
2)），1753（ν(-C=O)），1570（ν(C=N)/ν(C=C)），1468、1438（δ(CH
2)/δ
as(CH
3)），1352（ν(S=O)），1194（ν(C-F)），1138（δ(S=O)），1057（δ(C-F)）。
1HNMR（400MHZ:DMSO-d6;δ/ppm relative to TMS）
9.068（1H,s,NCHN），7.725（2H,s,NCH），5.252（2H,s,NCH2），4.123（2H,t,J=6.4HZ,-OCH2）,3.909（3H,s,NCH3）,1.635（2H,m,J=7.2HZ,CH2CH3）0.909（3H,t,J=7.2HZ,CH2CH3），
MS:m/z183.11(M
+)，279.92（NTf
2 -）
[CH
2C
6H
4COOCH
2CH
3MIM]NTf
2
IR,ν/cm
-1:3156、3119（ν(im-CH)/ν(PhH-CH)），2988、2909（ν
as(CH
3)/ν
as(CH
2)），1714（ν(C=O)），1615、1577（ν(C=N)/ν(C=C)），1451、1421（δ(CH
2)/δ
as(CH
3)），1352（ν(S=O)），1194（ν(C-F)），1136（δ(S=O)），1057（δ(C-F)）。
1HNMR（400MHZ:DMSO-d6;δ/ppm relative to TMS）
9.209（1H,s,NCHN），7.999（2H,d,J=8HZ,(CH)2），7.793（1H,s,NCH,），7.739（1H,s,NCH），7.525（2H,d,J=8HZ,(CH)2），5.520（2H,s,NCH2），4.317（2H,q,J=7.2HZ,-OCH2）3.861（3H,s,-NCH3），1.312(3H,t,J=7.2HZ,-OCH2CH3）MS:m/z245.13(M
+)，279.92（NTf
2 -）
Said structure appraising datum confirms that material of the present invention is 1-ethyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt, 1-n-propyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt and 1-ethyl p-methyl benzoate base-3-Methylimidazole bis trifluoromethyl sulfimide salt really.
Embodiment 4
Taking 1-ethyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt 15mg is coated on the white carrier of 100mg pickling 102, adopts passive sampling method to be enriched to volatility in air and semi-volatile organic compounds.
Embodiment 5
Taking 1-n-propyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt 15mg is coated on the white carrier of 100mg pickling 102, adopts passive sampling method to be enriched to volatility in air and semi-volatile organic compounds.
Embodiment 6
Taking 1-ethyl p-methyl benzoate base-3-Methylimidazole bis trifluoromethyl sulfimide salt 20mg is coated on the white carrier of 100mg pickling 102, adopts passive sampling method to be enriched to volatility in air and semi-volatile organic compounds.
Claims (1)
1. following selectivity ionic liquid is used for the extracting and enriching of contaminant trace species SVOCs in room air, selectivity ionic liquid is 1-ethyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt, 1-n-propyl acetate base-3-Methylimidazole bis trifluoromethyl sulfimide salt or 1-ethyl p-methyl benzoate base-3-Methylimidazole bis trifluoromethyl sulfimide salt, and its structural formula is as follows:
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