CN101723928A - Ion liquid and preparation technology thereof - Google Patents
Ion liquid and preparation technology thereof Download PDFInfo
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- CN101723928A CN101723928A CN200910252353A CN200910252353A CN101723928A CN 101723928 A CN101723928 A CN 101723928A CN 200910252353 A CN200910252353 A CN 200910252353A CN 200910252353 A CN200910252353 A CN 200910252353A CN 101723928 A CN101723928 A CN 101723928A
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Abstract
The invention relates to an ion liquid, a preparation method thereof and application of partial ion liquid in the invention. The ion liquid comprises crownether and salts. Particularly, the ion liquid comprises 18-crown-6, benzo-18-crown-6, bibenzo-18-crown-6, 15-crown-5, benzo-15-crown-5 and amino acid salt or organic acidic salt or inorganic salt or alkali.
Description
Technical field
The present invention relates to a class ionic liquid and an its preparation method, and the application of partial ion liquid among the present invention.
Background technology
Ionic liquid is made up of the ion and the electronegative ion of positively charged, refers to be when being lower than 100 degrees centigrade the fused salt of liquid state now more.In ionic liquid, there is not electroneutral molecule, the 100%th, negatively charged ion and positively charged ion, between negative 100 degrees centigrade to 200 degrees centigrade, all be liquid state, have good thermostability (decomposition temperature reaches 300 degrees centigrade) and electroconductibility, allow kinetic control to a great extent; Concerning most of inorganicss, organism and macromolecular material, ionic liquid is a kind of excellent solvent; Show acidity and super acids character, make it not only can be used as solvent and use, use but also can be used as some catalyst for reaction, the solvent of these catalytic activitys has avoided extra possible deleterious catalyzer maybe may produce the shortcoming of a large amount of wastes; Ionic liquid generally can not become steam (non-volatile or " zero " vapour pressure), so can not produce the obnoxious flavour that atmosphere is polluted in the chemical experiment process, this is the important evidence that ionic liquid is considered to green solvent; Price is relatively cheap, and most ionic liquids have stability to glassware for drinking water, prepare at aqueous phase easily; Ionic liquid also has good designability, can obtain the ionic liquid of specific function by molecular designing.In a word, ion liquid tasteless, ordorless, pollution-free, nonflammable, separate with product easily, easily reclaim that but repeated multiple times recycles, advantage such as easy to use, it is the ideal substitute of traditional volatile solvent, it has avoided the problems such as serious environmental that use causes, health, safety and equipment corrosion of conventional organic solvents effectively, is genuine, eco-friendly green solvent.Be suitable for the requirement of current cleaning technique of advocating and Sustainable development, more and more by the extensive recognition and acceptance of people.In addition, ionic liquid also has the following advantages: strong electrostatic field (this is the key character that is different from molecule-type medium and material); Wide electrochemical window (can reach 5V-7V) this means that electrochemical reaction can not take place ionic liquid in so wide scope, i.e. degraded, and this is the common not available characteristic of electrolytic solution; Good ionic conduction (25ms/cm) and thermal conductivity, high heat capacity and thermal energy storage density.
Ionic liquid is applied at the aspects such as preparation such as the catalytic hydrogenation reaction under rearrangement reaction, room temperature and the normal pressure of polyreaction, selective alkylation and amination reaction, acylation reaction, esterification, chemical bond, epoxidation Reaction of Alkenes, electrochemical synthesis, branched chain fatty acid, and demonstrates advantages such as speed of reaction is fast, transformation efficiency is high, the selectivity height of reaction, catalyst system repeated use capable of circulation.In addition, dissolving, nuclear fuel and the nuke rubbish of the extraction of ionic liquid carbonic acid gas in recovery, fuel cell and the solar cell of the separation of solvent extraction, material and purifying, spent high molecular compound, industrial gaseous waste, geological sample separate and aspect such as processing also demonstrates the potential application prospect.
Chinese invention patent application 95191587.8 discloses a kind of can be used as in the many kinds of hydrocarbon conversion reactions, the preparation method of ionic liquid of the catalyzer in alkylated reaction, oligomerisation reaction, isomerization reaction and the polyreaction for example, this method comprises: will be in ionic liquid the halide solution reaction of lead salt solution and required cationic in described ionic liquid of required cationic, separate consequent lead halide precipitation then to stay the solution of desired ion liquid.
China invention 02111687.3 open L-sulforamidate type chiral ionic liquid and preparation method thereof be with L-amino acid be made into the aqueous solution and concentration be 98% sulfuric acid fully react sulforamidate type chiral ionic liquid.
Summary of the invention
The invention provides a class ionic liquid that constitutes by crown ether, and this class preparation method of ionic liquid, several several application of ionic liquid in organic synthesis that constitute by crown ether provided simultaneously.Need to prove that especially by the prepared crown ether ionic liquid of the present invention can be chirality and achiral amino acid crown ether ionic liquid, it also can be the crown ether ionic liquid that constitutes by organic acid or salt or alkali, or the crown ether ionic liquid of simple inorganic salt formation, and the resulting crown ether ionic liquid great majority of the present invention are room temperature crown ether ionic liquid.
Ionic liquid of the present invention is to be made of crown ether and salt.
Say that more specifically ionic liquid of the present invention is by 18 hats 6 and benzo 18 hats 6 and dibenzo 18 is preced with 6 and 15 hats 5 and benzo 15 hats 5 constitute with amino acid salts; Its preparation method is to get amino acid, crown ether and potassium hydroxide or sodium hydroxide, in amino acid: alkali: the mol ratio of crown ether=1～1.2: 1: 0.8～1 ratio is dissolved in it in suitable quantity of water, stirred at normal temperatures 12 hours, remove water wherein, purify with ethanol, remove ethanol, drying is handled again, obtains purified transparent ionic liquid.
Ionic liquid of the present invention also can be by 18 hats 6 and benzo 18 hats 6 and dibenzo 18 is preced with 6 and 15 hats 5 and benzo 15 hats 5 constitute with organic acid salt; Its preparation method is to get organic acid, crown ether and potassium hydroxide or sodium hydroxide, in organic acid: alkali: the mol ratio=n of crown ether: 1: 1 ratio is dissolved in it in suitable quantity of water, wherein n is the number of carboxyl in the organic acid, stirred at normal temperatures 12 hours, remove wherein water and drying treatment, obtain purified transparent ionic liquid.
Ionic liquid of the present invention also can be to be made of the sylvite of 18 hats 6 and benzo 18 hat 6 and dibenzo 18 hats, 6 and 15 hats 5 and benzo 15 hats 5 and 12 hats 4 and amino acid/organic acid/mineral acid or sodium salt or lithium salts; Its preparation method is to get crown ether and sylvite or sodium salt or lithium salts, and in salt: the ratio of the mol ratio of crown ether=1: 1 is dissolved in it in suitable quantity of water, stirs at normal temperatures 12 hours, removes wherein water and dry, obtains purified transparent ionic liquid.
Ionic liquid of the present invention also can be to be made of crown ether and highly basic, in crown ether be 18 hats 6 and benzo 18 hat 6 and dibenzo 18 hats, 6 and 15 hats 5 and benzo 15 hats 5 and 12 hats 4, highly basic wherein is potassium hydroxide or sodium hydroxide or lithium hydroxide; Its preparation method is to get highly basic and crown ether, and in alkali: the ratio of the mol ratio of crown ether=1: 1 is dissolved in it in suitable quantity of water, stirs at normal temperatures 12 hours, removes wherein water and dry, obtains purified transparent ionic liquid.
The application of wherein a kind of chirality ionic liquid of the present invention is only to add propylene oxide and chiral ionic liquid in autoclave, and the capping still also charges into 0.6Mpa CO
2, the abundant reaction of warp can obtain the propylene cyclic carbonate ester of chirality.
The application of wherein a kind of ionic liquid of the present invention is with p-Nitrobromobenzene, vinylbenzene, N, dinethylformamide and ionic liquid [18-C-6]
3[PO
4], PdCl
2Add together in the reaction vessel, heat this mixture and stir down 3h at 110 ℃, separate the trans 1-phenyl of product-2-p-nitrophenyl ethene.
The application of wherein a kind of ionic liquid of the present invention is characterized in that adding cinnamophenone in reaction vessel, n-butyl mercaptan and ionic liquid [18-C-6K] [OAc] at room temperature stir after the 5min, extracted with diethyl ether, and use anhydrous Na
2SO
4Dry this diethyl ether solution, removing desolvates obtains white solid product 1, the positive butylthio propane of 3-phenylbenzene-3--1-ketone.
The application of wherein a kind of ionic liquid of the present invention is characterized in that adding benzhydrol and ionic liquid [18-C-6K] [BrO in the exsiccant reaction vessel
3], 120 ℃ of following stirring reactions, after reaction was finished, reaction mixture was washed with normal hexane, removed solvent and obtained the white solid product benzophenone.
The advantage of ionic liquid of the present invention is: 1, have all ion liquid characteristics; 2, preparation is simple; 3, can catalysis as catalyzer and promote many reactions to carry out fast; 4, easy purifying; 5, can do green solvent; 6, can repeatedly use repeatedly.Characteristics of the present invention are fairly obvious, ionic liquid different from the past, ionic liquid of the present invention is with crown ether the metal ion constraint to be formed chelating ion, and all in the past ionic liquids are pure organic ammonium salts form, mostly are the salt of substituted imidazole, pyridine etc.
Embodiment
Embodiments of the invention below are provided.
Embodiment 1
Get L-Histidine (L-His) (6mmol, 0.9310g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-His] [18-C-6K], and its structural formula is seen formula 1.
Formula 1
Embodiment 2
Get L-Methionin (L-Lys) (6mmol, 0.8771g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Lys] [18-C-6K], and its structural formula is referring to formula 2.
Formula 2
Embodiment 3
Get L-L-Ala (L-Ala) (6mmol, 0.5345g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Ala] [18-C-6K], and its structural formula is seen formula 3.
Formula 3
Embodiment 4
Get L-proline(Pro) (L-Pro) (6mmol, 0.6908g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Pro] [18-C-6K], and its structural formula is referring to formula 4.
Formula 4
Embodiment 5
Get L-phenylalanine (L-Phe) (6mmol, 0.9911g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Phe] [18-C-6K], and its structural formula is referring to formula 5.
Formula 5
Embodiment 6
Get L-tryptophane (L-Try) (6mmol, 1.2254g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Try[18-C-6K], and its structural formula is referring to formula 6.
Formula 6
Embodiment 7
Get L-leucine (L-Leu) (6mmol, 0.7871g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Leu] [18-C-6K], and its structural formula is referring to formula 7.
Formula 7
Embodiment 8
Get L-Serine (L-Ser) (6mmol, 0.6311g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Ser] [18-C-6K], and its structural formula is referring to formula 8.
Formula 8
Embodiment 9
Get L-Threonine (L-Thr) (6mmol, 0.7147g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid [L-Thr] [18-C-6K], and its structural formula is referring to formula 9.
Formula 9
Embodiment 10
Get L-methionine(Met) (L-Met) (6mmol, 0.8953g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Met] [18-C-6K], and its structural formula is referring to formula 10.
Formula 10
Embodiment 11
Get L-Xie Ansuan (L-Val) (6mmol, 0.7029g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent yellow hat worn by a Taoist priest ether ionic liquid [L-Val] [18-C-6K], and its structural formula is referring to formula 11.
Formula 11
Embodiment 12
Get L-L-glutamic acid (L-Glu) (3mmol, 0.4414g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Glu] [18-C-6K]
2, its structural formula is referring to formula 12.
Formula 12
Embodiment 13
Get L-Gelucystine (L-Cys) (3mmol, 0.72g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Cys] [18-C-6K]
2, its structural formula is referring to formula 13.
Formula 13
Embodiment 14
Get L-aspartic acid (L-Asp) (3mmol, 0.3993g), KOH (5mmol, 0.28g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Asp] [18-C-6K]
2, its structural formula is referring to formula 14.
Formula 14
Embodiment 15
Get L-Histidine (L-His) (6mmol, 0.9310g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-His] [15-C-5Na], and its structural formula is referring to formula 15.
Formula 15
Embodiment 16
Get L-Methionin (L-Lys) (6mmol, 0.8771g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Lys] [15-C-5Na], and its structural formula is referring to formula 16.
Formula 16
Embodiment 17
Get L-L-Ala (L-Ala) (6mmol, 0.5345g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Ala] [15-C-5Na], and its structural formula is referring to formula 17.
Formula 17
Embodiment 18
Get L-proline(Pro) (L-Pro) (6mmol, 0.6908g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Pro] [15-C-5Na], and its structural formula is referring to formula 18.
Formula 18
Embodiment 19
Get L-phenylalanine (L-Phe) (6mmol, 0.9911g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Phe[15-C-5Na], and its structural formula is referring to formula 19.
Formula 19
Embodiment 20
Get L-tryptophane (L-Try) (6mmol, 1.2254g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Try[15-C-5Na], and its structural formula is referring to formula 20.
Formula 20
Embodiment 21
Get L-leucine (L-Leu) (6mmol, 0.7871g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Leu] [15-C-5Na], and its structural formula is referring to formula 21.
Formula 21
Embodiment 22
Get L-Serine (L-Ser) (6mmol, 0.6311g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Ser] [15-C-5Na], and its structural formula is referring to formula 22.
Formula 22
Embodiment 23
Get L-Threonine (L-Thr) (6mmol, 0.7147g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid [L-Thr] [15-C-5Na], and its structural formula is referring to formula 23.
Formula 23
Embodiment 24
Get L-methionine(Met) (L-Met) (6mmol, 0.8953g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Met] [15-C-5Na].
Embodiment 25
Get L-Xie Ansuan (L-Val) (6mmol, 0.7029g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Val] [15-C-5Na].
Embodiment 26
Get L-L-glutamic acid (L-Glu) (3mmol, 0.4414g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Glu] [15-C-5Na]
2, its structural formula is referring to formula 24.
Formula 24
Embodiment 27
Get L-Gelucystine (L-Cys) (3mmol, 0.72g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Cys] [15-C-5Na]
2, its structural formula is referring to formula 25.
Formula 25
Embodiment 28
Get L-aspartic acid (L-Asp) (3mmol, 0.3993g), NaOH (5mmol, 0.20g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve to steam and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Asp] [15-C-5Na]
2, its structural formula is referring to formula 26.
Formula 26
Embodiment 29
Get citric acid (1.0mmol, 0.192g), KOH (3mmol, 0.168g), 18-C-6 (3mmol, 0.79g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 12h down, revolve steaming and dewater, 70 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid, and its structural formula is referring to formula 27.
Formula 27
Embodiment 30
Get the DL-oxysuccinic acid (1.5mmol, 0.201g), KOH (3mmol, 0.168g), 18-C-6 (3mmol, 0.79g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolve steaming and dewater, 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid, and its structural formula is referring to formula 28.
Formula 28
Embodiment 31
(2mmol, 0.149g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid to get KCl.
Embodiment 32
(2mmol, 0.332g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid to get KI.
Embodiment 33
(2mmol, 0.117g), (2mmol 0.44g) mixes and to be dissolved in the 15mL distilled water 15-C-5, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid to get NaCl.
Embodiment 34
(2mmol, 0.176g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid to get KOAc.
Embodiment 35
Get Sodium Glutamate (Na
2Glu) (3mmol), and 15-C-5 (6mmol, 1.32g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 8h down, revolves to steam to dewater, and 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent ionic liquid [Glu] [15-C-5Na]
2
Embodiment 36
Get K
2CO
3(2mmol, 0.276g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified faint yellow solid-state crown ether ionic liquid, mp.46-48 ℃.
Embodiment 37
Get KH
2PO
4(2mmol, 0.272g), 18-C-6 (2mmol, 0.528g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 38
(2mmol, 0.112g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid to get KOH.
Embodiment 39
Get KBrO
3(2mmol, 0.334g), 18-C-6 (2mmol, 0.528g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow solid, mp.112-115 ℃.
Embodiment 40
Get KClO
3(2mmol, 0.246g), 18-C-6 (2mmol, 0.528g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified colorless solid, mp.180-185 ℃.
Embodiment 41
(2mmol, 0.408g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified white solid, mp.128-130 ℃ to get Potassium Hydrogen Phthalate.
Embodiment 42
(2mmol, 0.238g), (2mmol 0.528g) mixes and to be dissolved in the 15mL distilled water 18-C-6, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified colorless solid, mp.178-180 ℃ to get KBr.
Embodiment 43
Get Na
2B
4O
7(2mmol, 0.402g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 44
(2mmol, 0.80g), (2mmol 0.44g) mixes and to be dissolved in the 15mL distilled water 15-C-5, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid to get NaOH.
Embodiment 45
Get K
2HPO
4(2mmol, 0.348g), 18-C-6 (4mmol, 1.056g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain white solid, mp.35-38 ℃.
Embodiment 46
Get K
3PO
4(2mmol, 0.414g), 18-C-6 (6mmol, 1.584g) mixing is dissolved in the 25mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain faint yellow solid, mp.35-38 ℃.
Embodiment 47
Get KHCO
3(2mmol, 0.200g), 18-C-6 (2mmol, 0.528g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain faint yellow solid, mp.113-116 ℃.
Embodiment 48
Get KNO
3(2mmol, 0.202g), 18-C-6 (2mmol, 0.528g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain white solid, mp.88-92 ℃.
Embodiment 49
(2mmol, 0.206g), (2mmol 0.44g) mixes and to be dissolved in the 15mL distilled water 15-C-5, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid to get NaBr.
Embodiment 50
Get Na
2SO
4(2mmol, 0.288g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 51
Get NaH
2PO
4(2mmol, 0.240g), 15-C-5 (2mmol, 0.44g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 52
Get Na
2SO
3(2mmol, 0.252g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 53
(2mmol, 0.164g), (2mmol 0.44g) mixes and to be dissolved in the 15mL distilled water 15-C-5, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid to get NaOAc.
Embodiment 54
Get Na
2C
2O
4(2mmol, 0.268g), 15-C-5 (4mmol, 0.88g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 55
Get NaIO
3(2mmol, 0.396g), 15-C-5 (2mmol, 0.44g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain white solid, mp.113-116 ℃.
Embodiment 56
Get LiCl (2mmol), 12-C-4 (2mmol) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 57
Get LiOH (2mmol), 12-C-4 (2mmol) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid.
Embodiment 58
Get LiBr (2mmol), 12-C-4 (2mmol) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 59
Get LiI (2mmol), 12-C-4 (2mmol) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 24h down, revolves to steam to dewater, and 80 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid.
Embodiment 60
Get Sodium Glutamate (Na
2Glu) (3mmol), and 15-C-5 (6mmol, 1.32g) mixing is dissolved in the 15mL distilled water, and normal temperature stirs 8h down, revolves to steam to dewater, and 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent ionic liquid [Glu] [15-C-5Na]
2
Embodiment 61
Get L-Histidine (L-His) (6mmol, 0.9310g), KOH (5mmol, 0.28g), B18-C-6 (4mmol, 1.404g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-His] [B18-C-6K], and its structural formula is referring to formula 29.
Formula 29
Embodiment 62
Get L-Methionin (L-Lys) (6mmol, 0.8771g), KOH (5mmol, 0.28g), DB18-C-6 (4mmol, 2.214g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain the transparent crown ether ionic liquid of purified orange [L-Lys] [DB18-C-6K], and its structural formula is referring to formula 30.
Formula 30
Embodiment 63
Get L-L-Ala (L-Ala) (6mmol, 0.5345g), KOH (5mmol, 0.28g), DB18-C-6 (4mmol, 2.214g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified faint yellow transparent crown ether ionic liquid [L-Ala] [DB18-C-6K], and its structural formula is referring to formula 31.
Formula 31
Embodiment 64
Get L-proline(Pro) (L-Pro) (6mmol, 0.6908g), KOH (5mmol, 0.28g), B15-C-5 (4mmol, 1.164g) mixing is dissolved in the 15mL distilled water, normal temperature stirs 12h down, revolve steaming and dewater, the unreacted amino acid in cooling back is separated out, and this mixture is dissolved in an amount of ethanol, the unreacted amino acid of elimination, remove ethanol, 70 ℃ of vacuum-drying 10h obtain purified yellow transparent crown ether ionic liquid [L-Pro] [B15-C-5K], and its structural formula is referring to formula 32.
Formula 32
Embodiment 65
(2.0mmol, 0.516g), (6mmol 1.32g) mixes and to be dissolved in the 15mL distilled water 15-C-5, and normal temperature stirs 12h down, revolves to steam to dewater, and 70 ℃ of vacuum-drying 10h obtain purified water white transparency crown ether ionic liquid to get trisodium citrate salt.
By above embodiment as seen, the present invention uses multiple amino acids, comprise chirality and achirality amino acid (α-, β-, and gamma-amino acid), multiple organic acid, comprise organic carboxyl acid, picric acid etc., with crown ether 18-C-6 or B18-C-6 or DB18-C-6 or 15-C-5 or B15-C-5,2 kinds of highly basic KOH, NaOH is as raw material; Or organic acid sodium salt and sylvite; Or the lithium salts of mineral acid, sodium salt and sylvite and crown ether 18-C-6 or B18-C-6 or DB18-C-6 or 15-C-5 or B15-C-5 or 12-C-4, be that solvent has prepared a series of room temperature crown ether ionic liquids with water.In a word, all compounds that contain lithium ion or sodium ion or potassium ion all can be prepared its new crown ether solvay-type salt with this method, and the fusing point of ionic liquid then depends on its anionic size and character.Below be the example that ionic liquid more of the present invention are used:
Application example 1
(the gloomy catalyzer of Jack's cloth)
Formula 33
In the 100mL autoclave, add propylene oxide (7mL, 100mmol), (R, R)-1 the gloomy catalyzer of Jack's cloth (0.0662g, 0.1mmol), chiral crown ether crown ether ionic liquid (product of embodiment 9) [18-C-6] [L-Thr] (0.0421g, 0.1mmol), the capping still also charges into 0.6Mpa CO
2, stir 12h under the room temperature.Discharge residual gas, underpressure distillation steams the water white transparency propylene carbonate, and its productive rate is 23.6%, and it is 62.6% that gas-chromatography is surveyed its enantiomeric excess value ee%, and its reaction formula is referring to formula 33.
Application example 2
In autoclave, only add propylene oxide and chiral crown ether crown ether ionic liquid [18-C-6] [L-Thr], the capping still also charges into 0.6Mpa CO
2, stir 24h under the room temperature, can obtain the propylene cyclic carbonate ester of 16.6%ee value.
Though it is relevant by CO
2The report for preparing cyclic carbonate ester with epoxy compounds is a lot, but by CO
2The report for preparing the optical purity cyclic carbonate ester with epoxy compounds is also few, and reported method mainly contains at present: CO
2Generate optically pure cyclic carbonate ester with optically pure epoxy reaction; Chirality salen is a Primary Catalysts, and achiral tetrabutyl ammonium halide (TBAX) or achiral phenyl trimethylammonium tribromide ammonium (PTAT) are promotor, common catalysis CO
2Generate optically pure cyclic carbonate ester with the racemic epoxide compound.This example is formed catalyst system with the amino acid crown ether ionic liquid of chirality salen and chirality and is come the above-mentioned reaction of catalysis, here the chirality of chirality Primary Catalysts and chirality promotor has an adduction effect in reaction, therefore just can obtain higher ee% under very gentle condition.Prepared chiral crown ether ionic liquid all can be used for the reaction of embodiment 1 and 2 from embodiment 1 to embodiment 30, and obtains good reaction result.
This example provides a method for preparing the high-optical-purity cyclic carbonate ester under mild conditions.
Application example 3
Formula 34
In the 25mL round-bottomed flask, and the adding p-Nitrobromobenzene (0.404g, 2mmol), vinylbenzene (0.26g, 2.5mmol), N, dinethylformamide (DMF) 2mL, prepared crown ether ionic liquid [18-C-6] among the embodiment 46
3[PO
4] (0.08g, 4mol%), K
2CO
3(0.414g, 3mmol), PdCl
2(0.0071g, 2mmol%).This mixture stirs 3h down at 110 ℃, and reaction process detects with thin-layer chromatography silica-gel plate (TLC).(3 * 10mL) extract the extraction liquid anhydrous Na to reaction mixture with ether
2SO
4Drying, removing desolvates obtains the trans 1-phenyl of yellow solid product-2-p-nitrophenyl ethene (0.43g, 96%).Reuse 5 times, productive rate keeps 95%, and its reaction formula is referring to formula 34.
In organic synthesis, the Heck reaction is the important carbon-carbon bond linked reaction of a class, in chemical industry, synthesis of natural product and synthetic active substance, be widely used in recent years, most Heck reaction is to carry out under the anhydrous and oxygen-free condition, it is easily synthetic that these impel people constantly to seek, high reactivity and the high catalyst system of stability.In this example, we use crown ether ionic liquid [18-C-6]
3[PO
4] as the part of palladium, obtain very high productive rate in the short period of time, and this catalyst system all is stable to empty G﹠W, reacting simple, easy to operate, can repeating is biggest advantage.
Application example 4
Formula 35
In the 25mL round-bottomed flask, and the adding cinnamophenone (0.416g, 2mmol), n-butyl mercaptan (0.234g, 2.6mmol), prepared crown ether ionic liquid [18-C-6K] [OAc] (0.94g, mixture 2.6mmol) among the embodiment 53.This mixture at room temperature stirs after the 5min, and (3 * 10mL) extract, and use anhydrous Na with ether
2SO
4Dry this diethyl ether solution.Removing desolvates obtains white solid product 1, the positive butylthio propane of 3-phenylbenzene-3--1-ketone (0.588,99%).Repeat to add reactant and carry out circulation experiment 10 times, productive rate keeps 98%, and purity is constant, and its reaction formula is referring to formula 35.
Mercaptan and a, the important method that forms the C-S key is not only in the Michael addition reaction of beta-unsaturated carbonyl compound, be widely used in the compound of biosynthesizing and synthetic bioactive, therefore grope gentle reaction conditions, seeking highly active catalyzer has very important meaning.This routine used crown ether ionic liquid [18-C-6K] [OAc] has high reactive behavior to the reaction of n-butyl mercaptan and cinnamophenone, and reactant almost completely transforms at reaction conditions extremely gentle in the extremely short time.In addition, this crown ether ionic liquid has also played solvent in reaction, and easily reclaims, and can recycle.
Application example 5
Formula 36
In the round-bottomed flask of exsiccant 10mL, add benzhydrol (0.552g, prepared crown ether ionic liquid [18-C-6K] [BrO 3mmol) and among the embodiment 39
3] (120 ℃ are stirred 2h down for 2.59g, mixture 6mmol), and reaction process detects with thin-layer chromatography silica-gel plate (TLC).After reaction was finished, reaction mixture was washed with normal hexane, removed solvent and obtained white solid product (0.49g, 91%), and its reaction formula is referring to formula 36.
Being oxidized to being reflected at of corresponding carbonyl compound by alcohol has important status in the organic chemistry, no matter be to fundamental research or to industrial production.The output of the annual carbonyl compound in the whole world is all 10
7More than the ton, wherein major part is to be got by pure and mild alkylaromatic hydrocarbon oxidation, and the oxygenant of seeking efficient stable will have great application.In this example, crown ether ionic liquid [18-C-6K] [BrO
3] not only make catalyzer but also make solvent, at short notice benzhydrol there is very high oxidation efficiency.And [18-C-6K] [BrO
3] very stable, therefore very easily operation of reaction.Embodiment 40 and 55 gained crown ether ionic liquid also can be used for this oxidizing reaction in addition, and productive rate is respectively 80% and 85%.
Claims (14)
1. an ionic liquid is characterized in that being made of crown ether and salt.
2. ionic liquid according to claim 1 is characterized in that by 18 hats 6 and benzo 18 hats 6 and dibenzo 18 is preced with 6 and 15 hats 5 and benzo 15 hats 5 constitute with amino acid salts.
3. the described preparation method of ionic liquid of claim 2, it is characterized in that getting amino acid, crown ether and potassium hydroxide or sodium hydroxide, in amino acid: alkali: the mol ratio of crown ether=1～1.2: 1: 0.8～1 ratio is dissolved in it in suitable quantity of water, stirred at normal temperatures 12 hours, remove water wherein, purify, remove ethanol with ethanol, drying is handled again, obtains purified transparent ionic liquid.
4. ionic liquid according to claim 1 is characterized in that being made of with organic acid salt 18 hats 6 and benzo 18 hat 6 and dibenzo 18 hats, 6 and 15 hats 5 and benzo 15 hats 5 by it is characterized in that.
5. the described preparation method of ionic liquid of claim 4, it is characterized in that getting organic acid, crown ether and potassium hydroxide or sodium hydroxide, in organic acid: alkali: the mol ratio=n of crown ether: 1: 1 ratio is dissolved in it in suitable quantity of water, wherein n is the number of carboxyl in the organic acid, stirred at normal temperatures 12 hours, remove wherein water and drying treatment, obtain purified transparent ionic liquid.
6. ionic liquid according to claim 1 is characterized in that being made of 18 hats 6 and benzo 18 hat 6 and dibenzo 18 hats, 6 and 15 hats 5 and benzo 15 hats 5 and 12 hats 4 and sylvite or sodium salt or lithium salts by it is characterized in that.
7. the described preparation method of ionic liquid of claim 6, it is characterized in that getting crown ether and sylvite or sodium salt or lithium salts, in salt: the ratio of the mol ratio of crown ether=1: 1 is dissolved in it in suitable quantity of water, stirs at normal temperatures 12 hours, remove wherein water and drying, obtain purified transparent ionic liquid.
8. an ionic liquid is characterized in that being made of crown ether and highly basic.
9. a kind of ionic liquid according to claim 8, it is characterized in that constituting by crown ether and highly basic, crown ether wherein is 18 hats 6 and benzo 18 hats 6 and dibenzo 18 hats, 6 and 15 hats 5 and benzo 15 hats 5 and 12 hats 4, and highly basic wherein is potassium hydroxide or sodium hydroxide or lithium hydroxide.
10. crown ether preparation method of ionic liquid, it is characterized in that getting highly basic and crown ether, in alkali: the ratio of the mol ratio of crown ether=1: 1 is dissolved in it in suitable quantity of water, stirs at normal temperatures 12 hours, remove wherein water and drying, obtain purified transparent ionic liquid.
11. the application of claim 2 or claim 4 or the described chirality ionic liquid of claim 6 is characterized in that only adding propylene oxide and chiral ionic liquid in autoclave, the capping still also charges into 0.6MpaCO
2, the abundant reaction of warp can obtain the propylene cyclic carbonate ester of chirality.
12. the application of the described wherein a kind of ionic liquid of claim 6 is characterized in that p-Nitrobromobenzene, vinylbenzene, N, dinethylformamide and ionic liquid [18-C-6]
3[PO
4], PdCl
2Add together in the reaction vessel, heat this mixture and stir down 3h at 110 ℃, separate the trans 1-phenyl of product-2-p-nitrophenyl ethene.
13. the application of the described wherein a kind of ionic liquid of claim 6 is characterized in that adding cinnamophenone in reaction vessel, n-butyl mercaptan and ionic liquid [18-C-6K] [OAc] at room temperature stir after the 5min, extracted with diethyl ether, and use anhydrous Na
2SO
4Dry this diethyl ether solution, removing desolvates obtains white solid product 1, the positive butylthio propane of 3-phenylbenzene-3--1-ketone.
14. the application of the described wherein a kind of ionic liquid of claim 6 is characterized in that adding benzhydrol and ionic liquid [18-C-6K] [BrO in the exsiccant reaction vessel
3], 120 ℃ of following stirring reactions, after reaction was finished, reaction mixture was washed with normal hexane, removed solvent and obtained the white solid product benzophenone.
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| CN101967126A (en) * | 2010-09-29 | 2011-02-09 | 彩虹集团公司 | Chiral leucine ion liquid |
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| CN101967126A (en) * | 2010-09-29 | 2011-02-09 | 彩虹集团公司 | Chiral leucine ion liquid |
| CN102956360A (en) * | 2011-08-17 | 2013-03-06 | 海洋王照明科技股份有限公司 | Capacitor electrolyte and capacitor using same |
| CN103880950A (en) * | 2014-02-08 | 2014-06-25 | 李美凤 | Method of extracting phycocyanin from ionic liquid aqueous two-phase system |
| CN103896868A (en) * | 2014-03-31 | 2014-07-02 | 兰州大学 | Preparation method of acidic aza-crown ether ionic liquid |
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| CN110396082A (en) * | 2019-08-08 | 2019-11-01 | 山西大学 | A kind of synthetic method of Azacrown ether containing functionalized ion liquid |
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| CN111218695B (en) * | 2020-02-18 | 2021-05-28 | 广西师范大学 | Method for realizing ketone alpha site methylation reaction under electrochemical condition |
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