CN106632056A - Preparation method of single crystal of alkynyl substituted imidazole ionic liquid - Google Patents

Preparation method of single crystal of alkynyl substituted imidazole ionic liquid Download PDF

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CN106632056A
CN106632056A CN201611225911.XA CN201611225911A CN106632056A CN 106632056 A CN106632056 A CN 106632056A CN 201611225911 A CN201611225911 A CN 201611225911A CN 106632056 A CN106632056 A CN 106632056A
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preparation
acetone
monocrystal
alkynyl substituted
liquid
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牟宗刚
罗锐亭
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University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a preparation method of a single crystal of alkynyl substituted imidazole ionic liquid. The preparation method comprises the following steps of (1), adding trimethylsilylimidazole and propargyl chloride, which are in a mole ratio of 1 to 2.2, into a three-mouth flask, using dichloromethane as a reaction solvent, and heating and refluxing an obtained first mixture for 24h; (2), carrying out ordinary distillation to distill off the dichloromethane at 40 DEG C, and distilling off a small quantity of the propargyl chloride, which is not reacted completely, at 58 DEG C; (3), carrying out reduced pressure distillation until no gas bubbles are generated, so as to obtain yellow viscous liquid; (4), adding saturated NaBF4 solution and 1,3-dialkynyl imidazole chloride, which are in a mole ratio of 1 to 1.1, into the three-mouth flask, using acetone as a reaction solvent, and agitating an obtained second mixture for 24 hours at a normal temperature; (5), filtering out a white deposit to obtain filter liquor, and washing the deposit for two to three times by using the acetone; (6), carrying out normal-pressure distillation and reduced pressure distillation successively to remove the solvent acetone, so as to obtain a yellowy solid, and culturing the single crystal with a volatilization method. The preparation method is mild in operation condition, simple in process, high in yield and stable in stability.

Description

A kind of preparation method of the imidazole ion liquid monocrystal of alkynyl substituted
Technical field
The present invention relates to a kind of synthesis of the imidazole ion liquid of alkynyl substituted of chemical field.
Background technology
Ionic liquid, because it has good stability and electric conductivity, not only may be used as the fuse salt under a kind of room temperature As environmentally friendly solvent, to be also used as catalyst and use, it is most important that the designability of ionic liquid, by dividing Son design obtains the ionic liquid of specific function.In recent years, the application of ionic liquid is more and more wider, and it is in solvent extraction, material Separation and purifying, the recovery of spent high molecular compound, fuel cell and solar cell, industrial waste gas in carbon dioxide The aspects such as the separation and process of extraction, the dissolving of geological sample, nuclear fuel and nuke rubbish show potential application prospect.
The content of the invention
The present invention devises a kind of imidazole ion liquid of new alkynyl substituted.
In order to achieve the above object, the technical solution used in the present invention is：The imidazole ion liquid monocrystal of alkynyl substituted Preparation method, it is characterised in that comprise the steps：
（1）It is 1 by mol ratio:2.2 TSIM and propargyl chloride are added in the there-necked flask of 100 mL, are added Dichloromethane is heated to reflux 24 h as reaction dissolvent, while magnetic agitation；
（2）Solution colour carries out gradually being changed into yellow from colourless with reaction, and viscosity becomes larger, and produces a small amount of drop to backflow anti- Should complete；
（3）Commonly distill and methylene chloride is evaporated off when 40 DEG C, unreacted complete a small amount of propargyl chloride is evaporated off when 58 DEG C；
（4）Vacuum distillation obtains Pale yellow viscous liquid to bubble-free generation；
（5）1,3- diynyl imidazoles villaumite is added in the there-necked flask of 100 mL, constant pressure funnel is slowly added to excessive saturation NaBF4Salting liquid, ratio is 1:1.1 acetone are stirred 24 hours as reaction dissolvent under normal temperature；
（6）Reaction being completely dissolved to solid completely, filtering out white precipitate and obtain filtrate, acetone washing precipitation two to three times must be filtered Liquid；
（7）Solvent acetone is removed under reduced pressure after first normal pressure, obtain faint yellow solid 1,3- diynyls tetrafluoroborate or hexafluoro Phosphate；
（8）By 1,3- diynyl tetrafluoroborate solid dissolvings in acetone hot solution, room temperature is cooled to, is sealed, stood Culture, to the monocrystal that culture is obtained X-ray diffraction analysis are carried out.
Operating condition of the present invention is gentle, and process is simple, high income, good stability.The miaow of the alkynyl substituted of present invention synthesis Oxazolinium ion liquid has wide application prospect for the recovery of the Noble Metal Rhodium in spent rhodium catalyst solution.
Description of the drawings
Accompanying drawing 1 is the crystal structure figure of 1,3- diynyl tetrafluoroborates；
Accompanying drawing 2, accompanying drawing 3, accompanying drawing 4, accompanying drawing 5 and accompanying drawing 6 are the crystal accumulation figures of 1,3- diynyl tetrafluoroborates.
Specific embodiment
With reference to examples of implementation, the invention will be further elaborated.
Case study on implementation 1
The preparation method of 1,3- diynyl tetrafluoroborate, comprises the steps：
（1）By 0.1 mol（15 mL）TSIM and 0.21 mol（About 18 mL）Propargyl chloride be added to 100 In the there-necked flask of mL, add the dichloromethane of 15 mL as reaction dissolvent, 24 h are heated to reflux, while magnetic agitation；
（2）Solution colour carries out gradually being changed into yellow from colourless with reaction, and viscosity becomes larger, and produces a small amount of drop to backflow anti- Should complete；
（3）Commonly distill and methylene chloride is evaporated off when 40 DEG C, unreacted complete a small amount of propargyl chloride is evaporated off when 58 DEG C.Subtract Pressure distillation is produced to bubble-free, the g of yellow viscous liquid 17.34 is obtained, yield is about 96%；
（4）The g of 1,3- diynyl imidazoles villaumite 3.12 is added in the there-necked flask of 100 mL, constant pressure funnel is slowly added to 1.98 The NaBF of g4Saturated salt solution, solution disappears after starting to become cloudy, with magnetic agitation during dropwise addition；
（5）Stop stirring after 2 h, add 30mL dichloromethane, shake up, stratification；
（6）The water on upper strata is extracted twice with 15ml/ dichloromethane, and the weak yellow liquid of lower floor is washed with 15ml/ distillation Wash twice, add 4.5 g anhydrous magnesium sulfates to be dried overnight；
（7）Filter, the filtrate decompression for obtaining is evaporated off dichloromethane, obtain 2.995 g faint yellow solids, yield is about 78%；
（8）0.46 g 1,3- diynyl tetrafluoroborate solid dissolvings are cooled in the acetone hot solution of 150 mL Room temperature, sealing, quiescent culture carries out X-ray diffraction analysis to the monocrystal that culture is obtained.
Case study on implementation 2
The preparation method of 1,3- diynyl tetrafluoroborate, bag following steps living：
（1）By 0.1 mol（15 mL）TSIM and 0.21 mol（About 18 mL）Propargyl chloride be added to 100 In the there-necked flask of mL, 24 h are heated to reflux, while magnetic agitation；
（2）Solution colour carries out gradually being changed into yellow from colourless with reaction, and viscosity becomes larger, and produces a small amount of drop to backflow anti- Should complete；
（3）Unreacted complete a small amount of propargyl chloride is evaporated off when 58 DEG C.Vacuum distillation obtains yellow and glues to bubble-free generation Property liquid 14.45g, yield is about 80%；
（4）The g of 1,3- diynyl imidazoles villaumite 3.3 is added in the there-necked flask of 100 mL, constant pressure funnel is slowly added to 2.03 g NaBF4Saturated salt solution, adds 80 mL acetone as reaction dissolvent, stirs 24 hours under normal temperature；
（6）White precipitate is filtered out, acetone washing precipitation two to three times obtains filtrate；
（7）Vacuum distillation after first normal pressure removes solvent acetone, obtains 3.84 g faint yellow solids 1,3- diynyl imidazoles tetrafluoro boron Hydrochlorate.Yield is about 91%；
（8）0.46 g 1,3- diynyl tetrafluoroborate solid dissolvings are cooled in the acetone hot solution of 150 mL Room temperature, sealing, quiescent culture carries out X-ray diffraction analysis to the monocrystal that culture is obtained.
Case study on implementation 3
The preparation method of 1,3- diynyl tetrafluoroborate, bag following steps living：
（1）By 0.1 mol（15 mL）TSIM and 0.21 mol（About 18 mL）Propargyl chloride be added to 100 In the there-necked flask of mL, add the dichloromethane of 15 mL as reaction dissolvent, 24 h are heated to reflux, while magnetic agitation；
（2）Solution colour carries out gradually being changed into yellow from colourless with reaction, and viscosity becomes larger, and produces a small amount of drop to backflow anti- Should complete；
（3）Commonly distill and methylene chloride is evaporated off when 40 DEG C, unreacted complete a small amount of propargyl chloride is evaporated off when 58 DEG C.Subtract Pressure distillation is produced to bubble-free, the g of yellow viscous liquid 17.34 is obtained, yield is about 96%；
（4）The g of 1,3- diynyl imidazoles villaumite 3.3 is added in the there-necked flask of 100 mL, constant pressure funnel is slowly added to 2.03 g NaBF4Saturated salt solution, adds 80 mL acetone as reaction dissolvent, stirs 24 hours under normal temperature；
（6）White precipitate is filtered out, acetone washing precipitation two to three times obtains filtrate；
（7）Vacuum distillation after first normal pressure removes solvent acetone, obtains 3.84 g faint yellow solids 1,3- diynyl imidazoles tetrafluoro boron Hydrochlorate.Yield is about 91%；
（8）0.46 g 1,3- diynyl tetrafluoroborate solid dissolvings are cooled in the acetone hot solution of 150 mL Room temperature, sealing, quiescent culture carries out X-ray diffraction analysis to the monocrystal that culture is obtained.
The difference of case study on implementation 3 and 1 is to replace dichloromethane with acetone in case study on implementation 2, substantially increases product Yield, is primarily due to acetone bigger for the solubility of purpose product；The difference of case study on implementation 3 and 2 is in case study on implementation 3 Dichloromethane is added as reaction dissolvent so that it is more complete that reaction is carried out.
The crystal data of 1,3- diynyl tetrafluoroborates：
Crystal Data. C9H9BF4N2, M =231.99, triclinic, a = 8.035(2) Å, b = 8.517 (2) Å, c = 9.757(3) Å, α = 74.07(2)°, β = 69.48(2)°, γ = 63.67(2)°, V = 554.8(2) Å3, T = 293.15, space group P-1 (no. 2), Z = 2, μ(Mo Kα) = 0.130, 4693 reflections measured, 2155 unique (R int = 0.0246) which were used in all calculations. The final wR 2 was 0.3324 (all data) and R 1 was 0.1045 (>2sigma (I))。

Claims (7)

1. the preparation method of the imidazole ion liquid monocrystal of a kind of alkynyl substituted, it is characterised in that comprise the steps：
（1）It is 1 by mol ratio:2.2 TSIM and propargyl chloride are added in the there-necked flask of 100mL, are added Dichloromethane is heated to reflux 24 h as reaction dissolvent, while magnetic agitation；
（2）Solution colour carries out gradually being changed into yellow from colourless with reaction, and viscosity becomes larger, and produces a small amount of drop to backflow anti- Should complete；
（3）Commonly distill and methylene chloride is evaporated off when 40 DEG C, unreacted complete a small amount of propargyl chloride is evaporated off when 58 DEG C；
（4）Vacuum distillation obtains yellow viscous liquid to bubble-free generation；
（5）1,3- diynyl imidazoles villaumite is added in the there-necked flask of 100mL, constant pressure funnel is slowly added to excessive saturation NaBF4Salting liquid, ratio is 1:1.1 acetone are stirred 24 hours as reaction dissolvent under normal temperature；
（6）Reaction being completely dissolved to solid completely, filtering out white precipitate and obtain filtrate, acetone washing precipitation two to three times must be filtered Liquid；
（7）Solvent acetone is removed under reduced pressure after first normal pressure, obtain faint yellow solid 1,3- diynyl tetrafluoroborates；
（8）Volatility process acetone soln culture monocrystalline.
2. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（1）The mol ratio of middle TSIM and propargyl chloride is 1: 2.2.
3. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（2）In slow heating backflow be stable at 51 ~ 54 DEG C.
4. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（1）With（5）Reaction time be 24 h.
5. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（5）Middle 1,3- diynyls imidazoles villaumite and saturation KPF6The ratio of salting liquid is 1: 1.1.
6. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（8）The culture of middle monocrystalline be by 1,3- diynyl tetrafluoroborate solid dissolvings in acetone hot solution, be cooled to room Temperature, sealing, quiescent culture.
7. the preparation method of the imidazole ion liquid monocrystal of alkynyl substituted according to claim 1, it is characterised in that：Step Suddenly（8）Middle culture obtains the X-ray diffraction analysis data of monocrystal and is：C9H9BF4N2, M =231.99, triclinic, a = 8.035(2) Å, b = 8.517(2) Å, c = 9.757(3) Å, α = 74.07(2)°, β = 69.48(2)°,γ = 63.67(2)°, V = 554.8(2) Å3, T = 293.15, space group P-1 (no. 2), Z = 2, μ(Mo Kα) = 0.130, 4693 reflections measured, 2155 unique (R int = 0.0246) which were used in all calculations. The final wR 2 was 0.3324 (all data) and R 1 was 0.1045 (>2sigma(I))。
CN201611225911.XA 2016-12-27 2016-12-27 Preparation method of single crystal of alkynyl substituted imidazole ionic liquid Pending CN106632056A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817785A (en) * 2003-08-26 2010-09-01 洛桑联邦理工学院 Ionic liquid based on the imidazoles that is combined with nitrile functionality

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817785A (en) * 2003-08-26 2010-09-01 洛桑联邦理工学院 Ionic liquid based on the imidazoles that is combined with nitrile functionality

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HARLOW K.J.ET AL.: "Convenient and General Synthesis of Symmetrical N,N-Disubstituted Imidazolium Halides", 《SYNTHESIS》 *
ZHAOFU FEI,ET AL.: "Organometallic Complexes Derived from Alkyne-Functionalized Imidazolium Salts", 《ORGANOMETALLICS》 *
崔美红: "含炔基离子液体的合成及性质", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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Application publication date: 20170510