CN1583726A - Chiral ion liquid of alkylimidazole tetrafluoroborate and its preparation - Google Patents
Chiral ion liquid of alkylimidazole tetrafluoroborate and its preparation Download PDFInfo
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- CN1583726A CN1583726A CN 03150455 CN03150455A CN1583726A CN 1583726 A CN1583726 A CN 1583726A CN 03150455 CN03150455 CN 03150455 CN 03150455 A CN03150455 A CN 03150455A CN 1583726 A CN1583726 A CN 1583726A
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- chiral
- alkyl
- chirality
- imidazoles
- ionic liquid
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- -1 tetrafluoroborate Chemical compound 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000007788 liquid Substances 0.000 title abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000005826 halohydrocarbons Chemical class 0.000 claims abstract description 7
- 239000002608 ionic liquid Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 abstract description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910020808 NaBF Inorganic materials 0.000 description 3
- 238000011914 asymmetric synthesis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000012069 chiral reagent Substances 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A chiral hydroxyimidazole tetrafluoroborate ion liquid is prepared from chiral alpha-phenethylamine, amonia water, ethanedial and formaldehyde through reacting to generate chiral-(alpha-methylbenzyl) imidazole, reacting on halohydrocarbon to generate chiral hydroxyimidazole quaternary ammonium salt, and reacting on tetrafluoroborate.
Description
Technical field
The present invention relates to a class chirality alkyl tetrafluoroborate ionic liquid and a preparation method, belong to new chemical material and preparation field thereof.
Background technology
Asymmetric synthesis has more and more caused the extensive concern of chemist, becomes an important component part in fields such as Synthetic Organic Chemistry, biological chemistry, medical chemistry and chemistry of pesticide.Usually, asymmetric catalysis synthesis is realized by using chiral auxiliary(reagent), chiral reagent and chiral catalyst.
Ionic liquid is called " planner's solvent " again, has been considered to a kind of novel dissolvent that has significant application value in the synthetic and cleaner production in green.The ion liquid synthetic and applied research in organic synthesis has had more report, wherein, the asymmetric catalysis synthesis research of carrying out in ionic liquid also has report, and its asymmetric synthesis realizes by adding chiral catalyst or chiral induction reagent in ionic liquid often.In recent years, people have begun to consider to utilize the characteristics of ionic liquid " designability ", and research is explored chiral ionic liquid and in Application for Field such as asymmetric organic synthesis.People such as Howarth design, have synthesized a kind of imidazole chiral ionic liquid (1) with two dissimilar chiral centreses, and are applied to Diels-Alder reaction (Tetrahedron Lett.1997,38,3097); People such as Seddon prepared BMI (lactate) the type chiral ionic liquid that negatively charged ion is a chirality (Green Chem.1999,23-25); Kitazume designs, has synthesized pyrrolidines chiral ionic liquid (2) (US 2001/0031875 A1); People such as Wasserscheid and Ishida designs respectively, synthetic chiral ionic liquid (3 and 4) has found potential application (Chem.Commun., 2002,200 on chiral recognition; WO 01/55060 A2) (Chem.Commun., 2002,2240); People such as He Mingyuan design, have synthesized a series of a-amino acid sulfate type chiral ionic liquids (CN 1383920A); Bao Wei very waits the people then to design, synthesized a series of bromination imidazole chiral ionic liquids (5) (J.Org.Chem., 2003,68,591) that contain hydroxyl.These achievements in research have been enriched ion liquid kind, have produced the new chemical material that a class had not only had the ionic liquid characteristic but also has chirality.But, the research work in this field just just begins, further explore new chiral ionic liquid, and then study it in Application for Field such as asymmetric organic syntheses, and the final novel chiral ionic liquid that obtains to have characteristic such as good asymmetric induction effect, will be important emerging research field in the modern synthetic chemistry.
Summary of the invention
The object of the present invention is to provide a class not only to have ion liquid general aspects, but also had the novel chiral alkyl tetrafluoroborate ionic liquid and the preparation method of chirality.
The ion liquid chemical structural formula of novel chiral alkyl tetrafluoroborate of the present invention is:
Wherein: it is the alkyl of 2-16 that R represents carbonatoms, comprises straight-chain alkyl or branched hydrocarbyl.In the chirality alkyl tetrafluoroborate ionic liquid of being invented, R is that the ionic liquid of ethyl and n-hexadecyl at room temperature is solid (fusing point is respectively 80 ℃ and 30 ℃), and all the other at room temperature are liquid, some in addition under-80 ℃, still do not solidify; Differential thermal analysis data presentation institute synthetic ionic liquid has thermostability preferably at 300 ℃ below the temperature; The ionic liquid of being invented all has opticity, and its specific rotation is 3-4 (C=4-4.5, ethanol) in the time of 25 ℃.
Novel chiral alkyl tetrafluoroborate preparation method of ionic liquid of the present invention is characterized in that: adopting chirality α-Ben Yian, ammoniacal liquor, oxalic dialdehyde and formaldehyde is starting raw material, at first synthesis of chiral N-(α-Jia Jibianji) imidazoles; Then, chirality N-(α-Jia Jibianji) imidazoles generates chirality alkyl imidazoles quaternary ammonium salt with halohydrocarbons reaction again; At last, chirality alkyl imidazoles quaternary ammonium salt and Tetrafluoroboric acid reactant salt generate the target chiral ionic liquid.Reaction principle is as follows:
In described chirality N-(α-Jia Jibianji) imidazoles synthetic, chirality α-Ben Yian: ammoniacal liquor: oxalic dialdehyde: the mol ratio of formaldehyde is 1: 1: 1: 1; Reaction times is 2-5h, and temperature of reaction is 60-100 ℃.
In described chirality alkyl imidazoles quaternary ammonium salt synthetic, halohydrocarbon is RX, and wherein to represent carbonatoms be the alkyl of 2-16 to R, comprises straight-chain alkyl or branched hydrocarbyl, X=Cl or Br or I, chirality N-(α-Jia Jibianji) imidazoles: the mol ratio of halohydrocarbon is 1: 1-1.5; Reaction times is 1-24h, and temperature of reaction is 50-110 ℃; Solvent for use can be acetonitrile or 1,2-ethylene dichloride or 1 or acetone or ethyl acetate or toluene, and wherein the amount ratio of reactant and solvent is 0.1-1mol/100mL.
In described target chiral ionic liquid synthetic, a tetrafluoro borate is MBF
4, wherein M=Li or Na or K or Ag or NH
4, chirality alkyl imidazoles quaternary ammonium salt: the mol ratio of a tetrafluoro borate is 1: 1; Reaction times is 1-24h, and temperature of reaction is 20-85 ℃; Solvent for use can be acetonitrile or 1,2-ethylene dichloride or 1 or acetone or ethyl acetate, and wherein the amount ratio of reactant and solvent is 0.1-1mol/100mL.
Novel chiral alkyl tetrafluoroborate ionic liquid of the present invention has following characteristics: both shown ion liquid general aspects, as under the room temperature being liquid, vapour pressure is zero, Heat stability is good, character such as good solubility; Show chirality again, as chiral separation, character such as chiral induction catalysis; So be expected to become the type material that actual application value is arranged in the fields such as Green Chemistry and asymmetric synthesis.Novel chiral alkyl tetrafluoroborate preparation method of ionic liquid of the present invention has following characteristics: reaction raw materials is easy to get, and is easy to operate, and preparation cost is cheap, and good product quality, yield height are fit to industrial production and application.
Embodiment
The preparation of embodiment 1. chirality N-(α-Jia Jibianji) imidazoles
With α-(+)-phenylethylamine (157.3g, optical purity＞99%, 1.3mol) and ammoniacal liquor (88.6g, 25-28% 1.3mol) mix, and its mixed solution is called solution A; With oxalic dialdehyde (188.6g,＞40%, 1.3mol) and formaldehyde (104.4g,＞37%, 1.3mol) mix, its mixed solution is called solution B.Drip simultaneously solution A and solution B from two dropping funnels, stir and keep down that reaction solution is little to boil in the 1L there-necked flask, about 1h dropwises, and stops behind the restir 1h under refluxing.Water pump removes water under reduced pressure, eliminate water after, change the oil pump distillage into, collect the cut of 150-160 ℃ (5-10mmHg), product be white to weak yellow liquid (190.1g, yield 85%), [α]
D 25=+1.858 (C=5.92, ethanol).
The preparation of embodiment 2. chirality alkyl imidazoles quaternary ammonium salts (R is a normal-butyl)
Add chirality N-(α-Jia Jibianji) imidazoles (S configuration in the 250mL there-necked flask; 34.7g; 0.2mol), bromination of n-butane (27.5g; 98%, 0.2mol) and toluene (40mL), back flow reaction 24h under nitrogen protection; topple over and remove toluene layer; (2 * 20mL), redistillation obtains target quaternary ammonium salt (58.4g, yield 94%) after taking off most solvent with the ethyl acetate washing.
The preparation of embodiment 3. chirality alkyl imidazoles quaternary ammonium salts (R is a n-octyl)
Add chirality N-(α-Jia Jibianji) imidazoles (S configuration in the 100mL there-necked flask; 17.4g; 0.1mol), n-octane bromide (19.3g; 98%, 0.1mol) and toluene (10mL), back flow reaction 20h under nitrogen protection; topple over and remove toluene layer; (2 * 20mL), redistillation obtains target quaternary ammonium salt (34.3g, yield 94%) after taking off most solvent with the ethyl acetate washing.
The preparation of embodiment 4. chirality alkyl imidazoles quaternary ammonium salts (R is a dodecyl)
Add chirality N-(α-Jia Jibianji) imidazoles (R configuration in the 100mL there-necked flask; 17.4g; 0.1mol), bromo n-dodecane (26.1g; 98%, 0.1mol) and toluene (20mL), back flow reaction 24h under nitrogen protection; topple over and remove toluene layer; (2 * 20mL), redistillation obtains target quaternary ammonium salt (40.4g, yield 96%) after taking off most solvent with the ethyl acetate washing.
The preparation of embodiment 5. chirality alkyl tetrafluoroborate ionic liquids (R is a normal-butyl)
Add in the 250mL there-necked flask chirality alkyl imidazoles quaternary ammonium salt (R is a normal-butyl) (58.4g, 0.188mol), NaBF
4(20.9g, 99%, 0.188mol) and acetone (100mL), back flow reaction 24h removes by filter inorganic salt under nitrogen protection, and distillation removes acetone, obtains target chiral ionic liquid (56.1g, yield 94%).Product still is flowable thick liquid after placing 24h under-80 ℃, [α]
D 25=-3.211 (C=4.36, ethanol).
The preparation of embodiment 6. chirality alkyl tetrafluoroborate ionic liquids (R is a n-octyl)
Add in the 250mL there-necked flask chirality alkyl imidazoles quaternary ammonium salt (R is a n-octyl) (34.3g, 0.094mol), NaBF
4(10.4g, 99%, 0.094mol) and acetonitrile (50mL), back flow reaction 20h removes by filter inorganic salt under nitrogen protection, and distillation removes acetonitrile, obtains target chiral ionic liquid (34.0g, yield 91%).Product still is flowable thick liquid after placing 24h under-80 ℃, [α]
D 25=-3.600 (C=4.16, ethanol).
The preparation of embodiment 7. chirality alkyl tetrafluoroborate ionic liquids (R is a dodecyl)
Add in the 250mL there-necked flask chirality alkyl imidazoles quaternary ammonium salt (R is a dodecyl) (40.4g, 0.096mol), NaBF
4(10.6g, 99%, 0.096mol) and 1 (50mL), back flow reaction 24h removes by filter inorganic salt under nitrogen protection, and distillation removes 1, obtains target chiral ionic liquid (40.4g, yield 98%).Product still is flowable thick liquid after placing 24h under-80 ℃, [α]
D 25=+3.326 (C=4.36, ethanol).
Claims (5)
1. novel chiral alkyl tetrafluoroborate ionic liquid, it is characterized in that: chiral ionic liquid has following chemical structural formula:
Wherein: it is the alkyl of 2-16 that R represents carbonatoms, comprises straight-chain alkyl or branched hydrocarbyl.
2. novel chiral alkyl tetrafluoroborate preparation method of ionic liquid is characterized in that: adopting chirality α-Ben Yian, ammoniacal liquor, oxalic dialdehyde and formaldehyde is starting raw material, at first synthesis of chiral N-(α-Jia Jibianji) imidazoles; Then, chirality N-(α-Jia Jibianji) imidazoles generates chirality alkyl imidazoles quaternary ammonium salt with halohydrocarbons reaction again; At last, chirality alkyl imidazoles quaternary ammonium salt and Tetrafluoroboric acid reactant salt generate the target chiral ionic liquid; The chemical equation in each step is:
3. preparation method as claimed in claim 2 is characterized in that: during synthesis of chiral N-(α-Jia Jibianji) imidazoles, chirality α-Ben Yian: ammoniacal liquor: oxalic dialdehyde: the mol ratio of formaldehyde is 1: 1: 1: 1; Reaction times is 2-5h, and temperature of reaction is 60-100 ℃.
4. preparation method as claimed in claim 2, it is characterized in that: during synthesis of chiral alkyl imidazoles quaternary ammonium salt, halohydrocarbon is RX, wherein to represent carbonatoms be the alkyl of 2-16 to R, comprise straight-chain alkyl or branched hydrocarbyl, X=Cl or Br or I, chirality N-(α-Jia Jibianji) imidazoles: the mol ratio of halohydrocarbon is 1: 1-1.5; Reaction times is 1-24h, and temperature of reaction is 50-110 ℃; Solvent for use can be acetonitrile or 1,2-ethylene dichloride or 1 or acetone or ethyl acetate or toluene.
5. preparation method as claimed in claim 2 is characterized in that: when synthesizing the target chiral ionic liquid, a tetrafluoro borate is MBF
4, wherein M=Li or Na or K or Ag or NH
4, chirality alkyl imidazoles quaternary ammonium salt: the mol ratio of a tetrafluoro borate is 1: 1; Reaction times is 1-24h, and temperature of reaction is 20-85 ℃; Solvent for use can be acetonitrile or 1,2-ethylene dichloride or 1 or acetone or ethyl acetate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150455 CN1235883C (en) | 2003-08-18 | 2003-08-18 | Chiral ion liquid of alkylimidazole tetrafluoroborate and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03150455 CN1235883C (en) | 2003-08-18 | 2003-08-18 | Chiral ion liquid of alkylimidazole tetrafluoroborate and its preparation |
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| Publication Number | Publication Date |
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| CN1583726A true CN1583726A (en) | 2005-02-23 |
| CN1235883C CN1235883C (en) | 2006-01-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891685A (en) * | 2010-07-16 | 2010-11-24 | 齐齐哈尔大学 | Alkyl imidazole-L-proline salt chiral ionic liquid and preparation method thereof |
| CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
| CN109053847A (en) * | 2018-07-18 | 2018-12-21 | 云南大学 | One kind 17 β-imidazolidinyl bromide-remove hydrogen meter androstane derivatives and its preparation method and application |
-
2003
- 2003-08-18 CN CN 03150455 patent/CN1235883C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891685A (en) * | 2010-07-16 | 2010-11-24 | 齐齐哈尔大学 | Alkyl imidazole-L-proline salt chiral ionic liquid and preparation method thereof |
| CN105903457A (en) * | 2016-06-12 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Imidazole ionic liquid chiral stationary phase and preparation method and application |
| CN109053847A (en) * | 2018-07-18 | 2018-12-21 | 云南大学 | One kind 17 β-imidazolidinyl bromide-remove hydrogen meter androstane derivatives and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1235883C (en) | 2006-01-11 |
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