CN1847201A - Amino group-containing chiral ionic liquid and its prepn process and application - Google Patents
Amino group-containing chiral ionic liquid and its prepn process and application Download PDFInfo
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- CN1847201A CN1847201A CN 200510050271 CN200510050271A CN1847201A CN 1847201 A CN1847201 A CN 1847201A CN 200510050271 CN200510050271 CN 200510050271 CN 200510050271 A CN200510050271 A CN 200510050271A CN 1847201 A CN1847201 A CN 1847201A
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- amino
- methyl
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 52
- 125000003277 amino group Chemical group 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 2
- -1 halogen ion Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 150000001413 amino acids Chemical class 0.000 claims abstract description 12
- 238000006957 Michael reaction Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001556 precipitation Methods 0.000 description 11
- 229940024606 amino acid Drugs 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000006837 decompression Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 6
- 229960002429 proline Drugs 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011914 asymmetric synthesis Methods 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- RGOMQUJTDIRXOC-UHFFFAOYSA-N [Br].CC1=NC=CN1C Chemical compound [Br].CC1=NC=CN1C RGOMQUJTDIRXOC-UHFFFAOYSA-N 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229930182821 L-proline Natural products 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-ZETCQYMHSA-N (S)-1-phenylethanol Chemical compound C[C@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-ZETCQYMHSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- KGWVFQAPOGAVRF-UHFFFAOYSA-N 1-hexylimidazole Chemical class CCCCCCN1C=CN=C1 KGWVFQAPOGAVRF-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KAIPJQCQNJYTCR-UHFFFAOYSA-N 1h-imidazol-1-ium;2,2,2-trifluoroacetate Chemical compound [NH2+]1C=CN=C1.[O-]C(=O)C(F)(F)F KAIPJQCQNJYTCR-UHFFFAOYSA-N 0.000 description 1
- YYXYOQCSQRSJTE-VQXHTEKXSA-N CCC(C)[C@@H](CN1C=CN(C1C)C)N Chemical compound CCC(C)[C@@H](CN1C=CN(C1C)C)N YYXYOQCSQRSJTE-VQXHTEKXSA-N 0.000 description 1
- YIKYPFPDGUJJMD-UHFFFAOYSA-N CN1C=NC=C1.[Br] Chemical compound CN1C=NC=C1.[Br] YIKYPFPDGUJJMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- YVLQQBDCKHOSBN-UHFFFAOYSA-N FC(C(=O)[O-])(F)F.CC1=[N+](C=CN1)C Chemical compound FC(C(=O)[O-])(F)F.CC1=[N+](C=CN1)C YVLQQBDCKHOSBN-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229940093740 amino acid and derivative Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012069 chiral reagent Substances 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 235000015177 dried meat Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RPMXALUWKZHYOV-UHFFFAOYSA-N nitroethene Chemical group [O-][N+](=O)C=C RPMXALUWKZHYOV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to amino group-containing chiral ionic liquid and its preparation process and application in organic asymmetrical catalytic Michael reaction. The chiral ionic liquid has the general expression of A+B-, A+ is shown, and B- is halogen ion or other negative ions as shown. The preparation process includes the following steps: the reflux reaction between amino acid derived halogenated fatty amine haloid and substituting imidazole in organic solvent, and the neutralization of the reacted liquid to obtain the product. The chiral ionic liquid with connected imidazole cycle possessing excellent stereo steric hindrance effect has excellent chiral catalytic performance on Michael reaction except its application as common ionic liquid.
Description
(1) technical field
The present invention relates to a kind of contain amino chiral ionic liquid, preparation method and application thereof.
(2) background technology
Asymmetric synthesis has become the important research direction of 21 century chemistry, is an indispensable integral 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.The catalysis asymmetric synthesis is optimal method of asymmetric synthesis, and it only uses a spot of chiral catalyst just to obtain a large amount of chiral product.Chiral catalyst can be divided into chirality organic coordination compound metal catalyst, enzyme and chirality organic molecule catalyzer, chirality organic molecule catalyzer is because it is environmentally friendly, do not use expensive transition metal and chiral ligand and be much accounted of day by day, especially since the nineties in last century, it has obtained many results of study with potential practical value in reactions such as asymmetric alkylation, reduction, epoxidation, Aldol, Mannich, Michael, Diels-Alder.
Amino acid and derivative thereof have plurality of advantages as chirality organic molecule catalyzer: amino acid is at first nontoxic, cheap and obtain easily; Natural amino acid optical purity height, kind is many; Can carry out chemically modified and obtain many chiral catalyst, part or intermediates that actual application value is arranged, as obtaining the product halo aliphatic amide halate that halogen replaces carboxyl by reduction, halogenation, be a good optical activity intermediate.Wherein proline(Pro) (1) is as a kind of simple in structure and nature content rich in amino acid, proline(Pro) and derivative thereof receive much concern as the research of catalyzer, and show extraordinary catalytic performance in multiple asymmetric catalysis (Tetrahedron, 2002,58,5573; Syn.Lett., 2001,1675).As far back as Wiechert group in 1971 was catalyzer with the proline(Pro) just, was used for the asymmetric Aldol reaction of intramolecularly (Angew.Chem.Int.Ed.Eng.1971,10,496).People such as Benaglia have synthesized the immobilized chiral catalyst (2) of polyoxyethylene glycol of solubility from oxyproline, use it for asymmetric aldol reaction, the ee value (enantiomeric excess value) of product can reach 77%, and catalytic activity slightly reduces when reclaiming repeated use.Corey etc. form the complex compound reduction of acetophenones with chirality dried meat ammonia alcohol (3) and borine, get (S)-1-phenylethyl alcohol, and productive rate is greater than 91%, and the ee value is 95% (J.Am.Chem.Soc., 1987,109,5551).Eddine etc. have reported and have utilized L-proline(Pro) deutero-tetramethyleneimine salt compounded of iodine (4) as chiral phase-transfer catalyst, under solid-liquid phase transfer reaction condition, the asymmetric alkylation reaction of aromatic imine generates has optically active primary amine, the ee value is at 90%～94% (Tetrahedron:Asymmetry, 1990,6,265).Hanessian in 2000 etc. have found asymmetric Michael Reaction (the Organic Lett. of L-proline(Pro) energy chirality catalysis 4-nitro alkyl and ketenes, 2000,2,2975), people such as Barbas utilizes (5) in asymmetric Michael addition reaction good catalytic effect to be arranged in the near future, and the ee value of product can reach 91% (Tetrahedron Lett., 2001,42,4441), also reported (6) asymmetric Michael Reaction to aldehyde and nitroethylene compounds the same period, product yield reaches 96%, diastereomer ratio is 98: 2, the ee value can reach 78%, but catalyst recovery is applied mechanically difficult (Organic Lett., 2001,3,3737).
Ionic liquid 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.Be organic micromolecule catalyst with the proline(Pro) especially, Aldol in ionic liquid reaction can obtain 71%ee value, but yield and ee value begin decline (Tetrahedron Lett.2002,43,8741) after repeating to apply mechanically four times.In recent years, people have begun to consider to utilize ionic liquid " designability " characteristics, research to explore 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 with two dissimilar chiral centreses, and are applied to Diels-Alder reaction (Tetrahedron Lett.1997,38,3097); People such as Seddon prepared the lactic acid type chiral ionic liquid that negatively charged ion is a chirality (Green Chem.1999,23-25); Kitazume designs, has synthesized pyrrolidines chiral ionic liquid (US 2001/0031875A1); People such as Wasserscheid and Ishida designs respectively, the synthetic chiral ionic liquid has found potential application (Chem.Commun., 2002,200 on chiral recognition; WO 01/55060 A2) (Chem.Commun., 2002,2240).
Making full use of amino acid whose advantage, is starting raw material and chiral source with amino acid, design, synthesizing new chiral ionic liquid, and the investigator has done some useful work both at home and abroad.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 utilize amino acid whose amino to synthesize imidazole ring, has designed, synthesized a series of bromination imidazole chiral ionic liquids (J.Org.Chem., 2003,68,591) that contain hydroxyl; People such as Hiroyuki are by ion-exchange, and having synthesized with amino acid is anionic glyoxaline ion liquid (J.Am.Chem.Soc., 2005,127,2398).These achievements in research have been enriched ion liquid kind, but, the research work in this field just just begins, further explore the new ionic liquid that the ionic liquid characteristic has chirality again that has, and then research and develop it in Application for Field such as asymmetric organic syntheses, and final obtain to have good asymmetric induction effect, be easy to the novel chiral ionic liquid that recovery set such as uses at characteristic, will be important emerging research field in the modern Green Chemistry.
(3) summary of the invention
The object of the present invention is to provide a kind of amino chiral imidazole type ionic liquid that contains.
Another object of the present invention is to provide the preparation method of above-mentioned chiral ionic liquid.
The present invention also provides the application of above-mentioned chiral ionic liquid in organic asymmetry catalysis Michael reaction.
For achieving the above object, the chiral ionic liquid that contains amino provided by the invention, its general formula is A
+B
-, described A
+Shown in (I);
Wherein, R
1For suc as formula (II) or the substituting group (III),
R
2For containing the saturated hydrocarbyl of 1～10 carbon atom, be preferably ethyl or hexyl;
R
3Be hydrogen or methyl or ethyl;
R
4Be the saturated hydrocarbyl or the benzyl of 1～5 carbon atom, be preferably one of following:
a、-CH
3；
b、-CH
2(CH
3)CH
2CH
3；
c、-CH
2(CH
3)CH
2CH
2CH
3；
d、-CH
2CH
2(CH
3)CH
2CH
3；
e、-CH
2Ph。
B
-Be halide-ions or one of following: CF
3COO
-, SO
4 2-, BF
4 -, SCN
-, PF
6 -, CF
3SO
3 -The preparation of described chiral ionic liquid is according to B
-Different and be divided into two portions, a part is preparation
B
-Be halide-ions X
-The quaterisation of chiral ionic liquid, another part is system father B
-Be non-halide-ions Y
-The replacement(metathesis)reaction of chiral ionic liquid.
B
-Be halide-ions X
-The preparation method of chiral ionic liquid as follows:
Suc as formula the amino acid derived halo aliphatic amide halate of (IV) with narrow azoles as the replacement of formula V and in organic solvent, carry out back flow reaction, reaction solution through neutralize described product;
HX·R
1-X
(IV) (V)
R wherein
1, R
2, R
3Define the samely, X is a halogen.
The described amino acid derived halo aliphatic amide halate and the molar ratio of substituted imidazole are preferably 0.5～1.9: 1.
It is one of following that described organic solvent is preferably: ethanol, acetonitrile, 1,2-ethylene dichloride, 1, toluene, acetone, more preferably ethanol.
The above-mentioned reaction times is generally a few hours to tens hour.
Chemical equation is:
Making B
-Be halide-ions X
-The basis of chiral ionic liquid on, can make B by the second step replacement(metathesis)reaction
-Be non-halide-ions Y
-Chiral ionic liquid, will contain amino chiral imidazole ammonium halide ionic liquid and contain B
-Be non-halide-ions Y
-Salt M
+Y
-Obtain chiral imidazole trifluoroacetate, vitriol, thiocyanate-, a tetrafluoro borate, hexafluorophosphate and fluoroform sulphonate ionic liquid, M through replacement(metathesis)reaction
+Be selected from Li
+, Na
+, K
+, Ag
+, NH
4 +Deng positively charged ion.
Chemical equation is:
Comprise in the object lesson of the present invention:
1-[(2S)-the 2-aminopropyl]-3-hexyl imidazoles bromine salt;
1-[(2S)-2-amino-3-methyl amyl]-2-methyl-3-Methylimidazole villaumite;
1-[(2S)-2-amino-4-methyl hexyl]-3-ethyl imidazol(e) bromine salt;
1-[(2S)-2-amino-3-methyl hexyl]-the 3-ethyl narrows azoles bromine salt;
1-[(2S)-2-amino-3-phenyl propyl]-3-Methylimidazole bromine salt;
1-[(S)-(2-pyrrolidyl) methyl]-the 3-ethyl narrows azoles bromine salt;
1-[(S)-(2-pyrrolidyl) methyl]-2-methyl-3-Methylimidazole bromine salt;
1-[(S)-(2-pyrrolidyl) methyl]-2-methyl-3-Methylimidazole trifluoroacetate;
1-[(S)-(2-pyrrolidyl) methyl]-3-ethyl imidazol(e) a tetrafluoro borate;
1-[(S)-(2-pyrrolidyl) methyl]-3-hexyl imidazoles hexafluorophosphate;
The ionic liquid of enumerating in the present invention all has opticity, and differential thermal analysis data presentation institute synthetic ionic liquid has thermostability preferably at 300 ℃ below the temperature, and is stable to water, almost do not have vapour pressure; Do not dissolve each other with non-polar solvent, can conveniently repeat to apply mechanically, have the amino that contains reactive hydrogen, chiral carbon is connecting fine inflexible imidazole ring, shows chirality, as chiral separation, character such as chiral induction catalysis show good chiral catalysis performance in the Michael reaction.As 1-[(2S)-the 2-aminopropyl]-3-hexyl imidazoles bromine salt; 1-[(S)-(2-pyrrolidyl) methyl]-3-ethyl imidazol(e) bromine salt; 1-[(S)-(2-pyrrolidyl) methyl]-right title Michael reactions such as 3-hexyl imidazoles hexafluorophosphate have good katalysis.Wherein pimelinketone and beta-nitrostyrene the reaction, under the room temperature with 1-[(S)-(2-pyrrolidyl) methyl]-3-ethyl imidazol(e) bromine salt is catalyzer, can reach 95% yield in 16 hours, d/r is 95: 5, can reach the 96%ee value.
Chiral ionic liquid of the present invention both can be used as ionic liquid and had used, do not dissolve each other with non-polar solvent, separate simple, can conveniently repeat to apply mechanically, because of having the imidazole ring that the active amino of substrate for induction, chiral carbon are being connected good sterically hindered effect is arranged again, and in the Michael reaction, show good chiral catalysis performance.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1 1-[(2S)-the 2-aminopropyl]-preparation of 3-hexyl imidazoles bromine salt
Add (S)-1-(brooethyl) ethylamine hydrobromide (22.12g in the 100mL there-necked flask, 0.1mol), N-hexyl imidazoles (15.51g, 98%, 0.1mol) and ethanol (60mL), back flow reaction 20h, decompression precipitation in neutralization back is with ethyl acetate washing (2 * 20mL), redistillation obtains target ammonium halide salt (27.55g, yield 95%) after taking off most solvent.
Embodiment 2 1-[(2S)-2-amino-3-methyl amyl]-preparation of 2-methyl-3-Methylimidazole villaumite
Add (S)-1-(chloromethyl)-2-3-methyl butylamine hydrochloride (17.37g in the 100mL there-necked flask, o.1mol), 1,2-methylimidazole (7.84g, 98%, 0.08mol) and acetonitrile (60mL), back flow reaction 40h, neutralization back decompression precipitation, (2 * 20mL), redistillation obtains target ammonium halide salt (16.67g, yield 90%) after taking off most solvent with the ethyl acetate washing.
Embodiment 3 1-[(2S)-2-amino-4-methyl hexyl]-preparation of 3-ethyl imidazol(e) bromine salt
Add (S)-1-(brooethyl)-3-dimethylpentylamine hydrobromate (26.36g in the 100mL there-necked flask, 0.1mol), N-ethyl imidazol(e) (10.78g, 98%, 0.11mol) and ethanol (60mL), back flow reaction 24h, decompression precipitation in neutralization back is with ethyl acetate washing (2 * 20mL), redistillation obtains target ammonium halide salt (26.50g, yield 96%) after taking off most solvent.
Embodiment 4 1-[(2S)-2-amino-3-methyl hexyl]-preparation of 3-ethyl imidazol(e) bromine salt
Add (S)-1-(brooethyl)-2-dimethylpentylamine hydrobromate (26.36g in the 100mL there-necked flask, 0.1mol), N-ethyl imidazol(e) (9.80g, 98%, 0.1mol) and ethanol (40mL), back flow reaction 20h, decompression precipitation in neutralization back is with ethyl acetate washing (2 * 20mL), redistillation obtains target ammonium halide salt (25.95g, yield 94%) after taking off most solvent.
Embodiment 5 1-[(2S)-2-amino-3-phenyl propyl]-preparation of 3-Methylimidazole bromine salt
Add (S)-1-(brooethyl)-2-phenyl-ethyl amine hydrobromate (29.80g in the 100mL there-necked flask, 0.1mol), N-Methylimidazole (12.55g, 98%, 0.15mol) and ethanol (40mL), back flow reaction 28h, decompression precipitation in neutralization back is with ethyl acetate washing (2 * 20mL), redistillation obtains target ammonium halide salt (27.23g, yield 92%) after taking off most solvent.
Embodiment 6 1-[(S)-(2-pyrrolidyl) methyl]-preparation of 3-ethyl imidazol(e) bromine salt
Add (2S)-2-(brooethyl) tetramethyleneimine hydrobromate (24.75g in the 100mL there-necked flask, 0.1mol), the N-ethyl narrows azoles (9.80g, 98%, 0.1mol) and ethanol (60mL), back flow reaction 24h, decompression precipitation in neutralization back is with ethyl acetate washing (2 * 20mL), redistillation obtains target ammonium halide salt (24.44g, yield 94%) after taking off most solvent.
Execute 7 1-[(S)-(2-pyrrolidyl) methyl]-preparation of 2-methyl-3-Methylimidazole bromine salt
Add (2S)-2-(brooethyl) tetramethyleneimine hydrobromate (24.75g in the 100mL there-necked flask, 0.1mol), 1,2-methylimidazole (9.80g, 98%, 0.1mol) and ethanol (60mL), back flow reaction 24h, neutralization back decompression precipitation, (2 * 20mL), redistillation obtains target ammonium halide salt (24.70g, yield 95%) after taking off most solvent with the ethyl acetate washing.
Embodiment 8 1-[(S)-(2-pyrrolidyl) methyl]-preparation of 2-methyl-3-Methylimidazole trifluoroacetate
Take by weighing 1-[(S)-(2-pyrrolidyl) methyl]-(13.14g 0.050mol), uses the 50mL water dissolution to 2-methyl-3-Methylimidazole bromine salt.Take by weighing silver suboxide (5.85g, 99%, 0.025mol) join in the 250mL there-necked flask, reenter and add trifluoracetic acid (5.76g, 99%, the aqueous solution of 100mL 0.050mol), after stirring to clarify, slowly add 1-[(S)-(2-pyrrolidyl) methyl]-aqueous solution of 2-methyl-3-Methylimidazole bromine salt, generate the Silver monobromide precipitation, stirring reaction 1h, remove by filter precipitation, underpressure distillation removes water, obtains target chiral ionic liquid (14.36g, yield 98%).
Embodiment 9 1-[(S)-(2-pyrrolidyl) methyl]-preparation of 3-ethyl imidazol(e) a tetrafluoro borate
Take by weighing 1-[(S)-(2-pyrrolidyl) methyl]-(13.14g 0.050mol), uses the 50mL water dissolution to 3-ethyl imidazol(e) bromine salt.Take by weighing silver suboxide (5.85g, 99%, 0.025mol) join in the 250mL there-necked flask, reenter and add HBF4 (4.47g, 98%, the aqueous solution of 100mL 0.050mol), after stirring to clarify, slowly add 1-[(S)-(2-pyrrolidyl) methyl]-aqueous solution of 3-ethyl imidazol(e) bromine salt, generate the Silver monobromide precipitation, stirring reaction 1h, remove by filter precipitation, underpressure distillation removes water, obtains target chiral ionic liquid (13.07g, yield 98%).
Embodiment 10 1-[(S)-(2-pyrrolidyl) methyl]-preparation of 3-hexyl imidazoles hexafluorophosphate
Add 1-[(S in the 100mL there-necked flask)-(2-pyrrolidyl) methyl]-the 3-hexyl narrows azoles bromine salt (15.96g, 0.050mol) KPF
6(9.29g, 99%, 0.050mol) and acetone (60mL),, remove by filter inorganic salt at room temperature reaction 48h, distillation removes acetone, obtains target chiral ionic liquid (19.95g, yield 95%).
Embodiment 11 1-[(2S)-the 2-aminopropyl]-application of 3-hexyl imidazoles bromine salt in the Michael reaction
Add 1-[(2S in two mouthfuls of flasks of 20mL)-the 2-aminopropyl]-3-hexyl imidazoles bromine salt (0.32g, 0.001mol), beta-nitrostyrene (0.752g, 99%, 0.005mol), pimelinketone (0.600g, 98%, 0.010mol) and 1-methyl-3-hexyl imidazoles hexafluorophosphate (4g), at room temperature reaction 10h, (3 * 20mL), distillation removes solvent to ethyl acetate extraction, obtains target product (2S
*)-2-((1R
*)-1-phenyl-2-nitro-ethyl) pimelinketone (1.21g, yield 97%, d/r are 90: 10, ee value 88%).
Embodiment 12 1-[(S)-(2-pyrrolidyl) methyl]-application of 3-hexyl imidazoles hexafluorophosphate in the Michael reaction
Add 1-[(S in two mouthfuls of flasks of 20mL)-(2-pyrrolidyl) methyl]-3-hexyl imidazoles hexafluorophosphate (0.32g, 0.001mol), beta-nitrostyrene (0.752g, 99%, 0.005mol), pimelinketone (0.600g, 98%, 0.010mol) and 1-methyl-3-hexyl imidazoles hexafluorophosphate (4g), at room temperature reaction 16h, (3 * 20mL), distillation removes solvent to ethyl acetate extraction, obtains target product (2S
*)-2-((1R
*)-1-phenyl-2-nitro-ethyl) pimelinketone (1.18g, yield 95%, d/r are 95: 5, ee value 96%).
Claims (10)
1, a kind of chiral ionic liquid that contains amino, its general formula is A
+B
-, described A
+Shown in (I):
Wherein, R
1For suc as formula (II) or the substituting group (III),
R
2For containing the saturated hydrocarbyl of 1～10 carbon atom, R
3Be hydrogen or methyl or ethyl, R
4Be the saturated hydrocarbyl or the benzyl of 1～5 carbon atom;
B
-Be halide-ions or one of following: CF
3COO
-, SO
4 2-, BF
4 -, SCN
-, PF
6 -, CF
3SO
3 -
2, the chiral ionic liquid that contains amino as claimed in claim 1 is characterized in that described R
4For one of following:
a、-CH
3；
b、-CH
2(CH
3)CH
2CH
3；
c、-CH
2(CH
3)CH
2CH
2CH
3；
d、-CH
2CH
2(CH
3)CH
2CH
3；
e、-CH
2Ph。
3, the chiral ionic liquid that contains amino as claimed in claim 1 or 2 is characterized in that described R
2Be ethyl or hexyl.
4, the chiral ionic liquid that contains amino as claimed in claim 1 is characterized in that described B
-Be halide-ions.
5, the chiral ionic liquid that contains amino as claimed in claim 4 is characterized in that described B
-Be Br
-
6, the described preparation method who contains amino chiral ionic liquid of a kind of claim 4, comprise the steps: in organic solvent, to carry out back flow reaction suc as formula the amino acid derived halo aliphatic amide halate of (IV) and substituted imidazole as formula V, reaction solution through neutralize described product;
HX·R
1-X
(IV) (V)
R wherein
1, R
2, R
3Definition is with claim 1, and X is a halogen.
7, as containing the preparation method of amino chiral ionic liquid as described in the claim 6, it is characterized in that the described amino acid derived halo aliphatic amide halate and the molar ratio of substituted imidazole are 0.5～1.9: 1.
8,, it is characterized in that described organic solvent is one of following: ethanol, acetonitrile, 1,2-ethylene dichloride, 1, toluene, acetone as containing the preparation method of amino chiral ionic liquid as described in the claim 6.
9, as containing the preparation method of amino chiral ionic liquid as described in the claim 8, it is characterized in that described organic solvent is an ethanol.
10, the described application of chiral ionic liquid in organic asymmetry catalysis Michael reaction that contains amino of claim 1.
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| CN101182308B (en) * | 2006-11-13 | 2010-06-09 | 浙江工业大学 | Imidazole chiral ionic liquids containing double function groups as well as preparation method and uses thereof |
| EP2223915A1 (en) | 2009-02-25 | 2010-09-01 | Dublin City University | Ionic liquid solvents |
| CN101954296A (en) * | 2010-09-29 | 2011-01-26 | 上海迎君化学科技有限公司 | Chiral catalyst for asymmetric Michael addition reaction and preparation method thereof |
| CN102643236A (en) * | 2012-02-21 | 2012-08-22 | 浙江师范大学 | Method for preparing chiral amide imidazolium bromide ionic liquid from natural amino acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2243539A3 (en) * | 2002-04-05 | 2011-06-01 | University Of South Alabama | Functionalized ionic liquids, and methods of use thereof |
| TW200526587A (en) * | 2003-09-05 | 2005-08-16 | Univ Alabama | Ionic liquids containing secondary hydroxyl-groups and a method for their preparation |
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| CN101182308B (en) * | 2006-11-13 | 2010-06-09 | 浙江工业大学 | Imidazole chiral ionic liquids containing double function groups as well as preparation method and uses thereof |
| EP2223915A1 (en) | 2009-02-25 | 2010-09-01 | Dublin City University | Ionic liquid solvents |
| WO2010097412A1 (en) | 2009-02-25 | 2010-09-02 | Dublin City University | Ionic liquid solvents |
| CN101954296A (en) * | 2010-09-29 | 2011-01-26 | 上海迎君化学科技有限公司 | Chiral catalyst for asymmetric Michael addition reaction and preparation method thereof |
| CN101954296B (en) * | 2010-09-29 | 2012-07-04 | 上海迎君化学科技有限公司 | Chiral catalyst for asymmetric Michael addition reaction and preparation method thereof |
| CN102643236A (en) * | 2012-02-21 | 2012-08-22 | 浙江师范大学 | Method for preparing chiral amide imidazolium bromide ionic liquid from natural amino acid |
| CN104324585A (en) * | 2014-11-05 | 2015-02-04 | 朱忠良 | Method for purifying blast furnace flue gas by using ionic liquid |
| CN104386733A (en) * | 2014-11-05 | 2015-03-04 | 朱忠良 | Synthesis method of nano cupric sulfide |
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| CN112844478A (en) * | 2021-01-04 | 2021-05-28 | 北京化工大学 | Preparation method and application of chiral two-dimensional material based on polyacid intercalation layered silicate |
| CN112844478B (en) * | 2021-01-04 | 2023-05-26 | 北京化工大学 | Preparation method and application of chiral two-dimensional material based on polyacid intercalation layered silicate |
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