CN103497160A - Chiral amine functional ionic liquid and preparation thereof - Google Patents
Chiral amine functional ionic liquid and preparation thereof Download PDFInfo
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- CN103497160A CN103497160A CN201310439053.9A CN201310439053A CN103497160A CN 103497160 A CN103497160 A CN 103497160A CN 201310439053 A CN201310439053 A CN 201310439053A CN 103497160 A CN103497160 A CN 103497160A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000001412 amines Chemical class 0.000 title abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 18
- 239000007859 condensation product Substances 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- -1 amino hexamethylene t-butyl carbamate Chemical compound 0.000 claims description 5
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000010511 deprotection reaction Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 abstract 1
- RWHIKEMYOLGZOC-UHFFFAOYSA-N 1h-imidazole-2-sulfonyl chloride Chemical compound ClS(=O)(=O)C1=NC=CN1 RWHIKEMYOLGZOC-UHFFFAOYSA-N 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- 238000005406 washing Methods 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 0 CS(c1ncc[n]1*)(=O)=O Chemical compound CS(c1ncc[n]1*)(=O)=O 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- FOEYMRPOKBCNCR-UHFFFAOYSA-N C(C1)C11CCCCC1 Chemical compound C(C1)C11CCCCC1 FOEYMRPOKBCNCR-UHFFFAOYSA-N 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- APHRGGHMFATICS-UHFFFAOYSA-N CCCCC[n+]1(C)c(CS(NC2CCCCC2)(=O)=O)[n](CCC)cc1 Chemical compound CCCCC[n+]1(C)c(CS(NC2CCCCC2)(=O)=O)[n](CCC)cc1 APHRGGHMFATICS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QASKCGNZJHBTDJ-UHFFFAOYSA-N [SiH4].BrCCCCC Chemical compound [SiH4].BrCCCCC QASKCGNZJHBTDJ-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/84—Sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the fields of a novel chemical material and a preparation technology thereof, and provides a chiral amine functional ionic liquid which is obtained by carrying out a condensation reaction on chiral hexamethylene diamine and imidazole sulfonyl chloride and then reacting a condensation product with halogenated hydrocarbon, and a preparation method thereof. The ionic liquid has the structural formula I as shown in the specification, in the formula, R1 is an aliphatic chain of C1-C4, R2 is the aliphatic chain of C1-C5, X<-> is Br<->, BF4<->, PF6<->, NTf2<->, OAc<->, and the like. The chiral ionic liquid is simple is simple in a preparation process, has double chiral spatial induction catalytic performance, and can be used in organic synthesis as an efficient chiral catalyst.
Description
Technical field:
The present invention relates to new chemical material and preparing technical field, specifically, relate to a kind of chiral ionic liquid and preparation method thereof.
Background technology:
In the past few decades, ionic liquid has a very wide range of applications in organic synthesis and separation and purification field as reaction medium and catalyzer.As everyone knows, ionic liquid is to consist of organic cation and inorganic or organic anion, under room temperature or near room temperature, is the salt of liquid state.Ionic liquid has the advantages such as low volatility, low melting point, structure designability, broadening window, good conductivity and good solubility energy, and it all is widely used in every field.Chinese patent CN101148392, CN1563008, CN1810757, CN1712093 etc. have set forth the application of ionic liquid in extracting and separating.Chinese patent CN101177252, CN11600429, CN101177299 etc. are successfully applied to field of nanometer technology by ionic liquid.Chinese patent CN101164122, CN101248495 etc. have reported applicable cases prepared at electro-conductive material and conducting film by ionic liquid.Along with the requirement of the optical purity of the new drug to newly developed improves day by day, the exploitation of chiral catalyst is more and more paid attention to by chemists.Therefore the chirality function ionic liquid of development of new becomes when last very critical task.Because the sulfonamides material is a kind of outstanding hydrogen bond donor, the chiral ionic liquid in conjunction with preparing of it and proline(Pro) demonstrates good catalytic activity (Org.Lett.2009,11,1037.) in asymmetric Michael addition.Yet the chirality function ionic liquid that as far as we know, sulfonamides material and the condensation of chirality cyclohexanediamine produce is reported there are no the people.Consider the three-dimensional inducibility that the chirality cyclohexanediamine is outstanding, we are necessary to prepare the chirality function ionic liquid of sulfonamides material and chirality cyclohexanediamine condensation generation.
Summary of the invention
It is a kind of by the generation condensation reaction of chirality cyclohexanediamine and imidazoles SULPHURYL CHLORIDE that the object of the invention has been to provide, and condensation product is by with halogenated alkane, reacting and obtain chiral ionic liquid, and the preparation method of this class ionic liquid is provided.
According to an aspect of the present invention, the invention provides a kind of with the amino hexamethylene t-butyl carbamate of (1R, 2R)-2-the chirality function ionic liquid with condensation product basis with the imidazoles SULPHURYL CHLORIDE, described chirality function ionic liquid has following structural formula I:
Wherein, R
1for the aliphatic chain of C1～C4, R
2for the aliphatic chain of C1～C5, X
--for Br
--, BF
4 --, PF
6 --, NTf
2 -, OAc
-.
Wherein, described R
1the aliphatic chain of C1～C4 be CH
3, CH
3cH
2, CH
3cH
2cH
2, and CH
3cH
2cH
2cH
2.
Wherein, described R
2the aliphatic chain of C1～C5 be CH
3, CH
3cH
2, CH
3cH
2cH
2, CH
3cH
2cH
2cH
2and CH
3cH
2cH
2cH
2cH
2.
Preferably, described chirality function ionic liquid is:
According to an aspect of the present invention; the invention provides a kind of preparation method of chirality function ionic liquid; wherein; (1R; the amino hexamethylene t-butyl carbamate of 2R)-2-with the imidazoles SULPHURYL CHLORIDE, in temperature of reaction, be to carry out condensation reaction under 0～30 ℃; the condensation product obtained reacts with halogenated alkane, ion exchange reaction and deprotection reaction obtain described chirality function ionic liquid, and its reaction equation is as follows:
Wherein, R
1for the aliphatic chain of C1～C4, R
2for the aliphatic chain of C1～C5, X
--for Br
--, BF
4 --, PF
6 --, NTf
2 -, OAc
-.
Wherein, described R
1the aliphatic chain of C1～C4 be CH
3, CH
3cH
2, CH
3cH
2cH
2, and CH
3cH
2cH
2cH
2.
Wherein, described R
2the aliphatic chain of C1～C5 be CH
3, CH
3cH
2, CH
3cH
2cH
2, CH
3cH
2cH
2cH
2and CH
3cH
2cH
2cH
2cH
2.
The intermediate of preparation and chiral ionic liquid are used
1h NMR,
13c NMR structural confirmation.
Compared to the prior art novel ion liquid provided by the invention and preparation method thereof, has following unusual effect:
(1) the present invention is to provide a kind of novel ion liquid, developed the new variety of ionic liquid;
(2) new function ionic liquid provided by the invention has chiral configuration, possesses outstanding dual stereoselectivity catalytic activity, can be used as from now in a kind of chiral catalyst application asymmetry catalysis.
Embodiment
Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are only for technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Add (1R in 250 milliliters of there-necked flasks, the amino hexamethylene t-butyl carbamate of 2R)-2-1 (7.1g, 33mmol), triethylamine (3.6g, 36mmol) and methylene dichloride (50mL), 0 ℃ of left and right starts to drip the dichloromethane solution (30mL) of 1-methyl-2-SULPHURYL CHLORIDE imidazoles 2 (6g, 33mmol).After dripping end, room temperature reaction 2 hours, TLC point plate reacts completely, and washing, then use dichloromethane extraction, merges organic phase, uses anhydrous sodium sulfate drying, filters, and removes solvent under reduced pressure, and column chromatography for separation obtains white solid 3 (11.3g), yield 96%.Reaction formula is:
1H?NMR(400MHz,CDCl
3)(ppm):1.05-1.31(m,4H),1.43(s,9H),1.55-1.63(m,2H),1.76-1.83(m,2H),2.28-2.37(m,1H),2.95-3.01(m,1H),3.83(s,3H),6.96(s,1H),7.33(s,1H);
13C?NMR(100MHz,CDCl
3)(ppm):156.9,126.3,123.9,119.5,79.2,56.8,54.9,35.8,32.7,28.1,24.7,24.3.
Add condensation product 3 (3.58g, 10mmol) in 250 milliliters of there-necked flasks, methyl iodide (1.86mL, 30mmol) and toluene (40mL), reflux 6 hours, and TLC detects, and reaction completes.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 4 (4.35g), yield 87%.Reaction formula is:
1H?NMR(400MHz,CDCl
3)(ppm):1.12-1.44(m,4H),1.42(s,9H),1.45-1.58(m,2H),1.78-1.83(m,2H),2.23-2.38(m,1H),3.01-3.08(m,1H),3.89(s,3H),3.95(s,3H),7.05(s,1H),7.41(s,1H);
13C?NMR(100MHz,D
2O)(ppm):157.1,125.9,125.1,120.5,80.3,56.9,53.8,35.8,34.7,33.4,29.5,25.3,24.2.
Add 4 (5.0g, 10mmol), NaBF in 100 milliliters of there-necked flasks
4(1.09g, 10mmol) and dehydrated alcohol (50mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 5 (4.71g), yield 91%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.15-1.41(m,4H),1.45(s,9H),1.43-1.69(m,4H),2.32-2.39(m,1H),2.95-3.06(m,1H),3.93(s,3H),4.01(s,3H),7.11(s,1H),7.38(s,1H);
13C?NMR(100MHz,D
2O)(ppm):158.3,125.6,125.5,118.3,82.1,56.6,52.2,36.8,33.2,31.4,28.8,26.3,25.6.
Add 5 (2.3g, 5mmol), the 4M hydrochloric acid dioxane aqueous solution (20 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 6 (1.67g), yield 93%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.01-1.23(m,4H),1.53-1.64(m,4H),1.75(d,1H,J=12.8Hz),1.78(d,1H,J=12.8Hz),2.36-2.38(m,1H),2.70-2.75(m,1H),3.92(s,3H),3.96(s,3H),6.99(s,1H),7.36(s,1H);
13C?NMR(100MHz,D
2O)(ppm):127.6,124.3,119.2,68.8,67.0,66.5,31.2,29.7,24.9,24.6.
Embodiment 2
Add 4 (5.0g, 10mmol), LiNTf in 100 milliliters of there-necked flasks
2(2.87g, 10mmol) and dehydrated alcohol (50mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃,
5 hours) obtain yellow oily liquid 7 (6.06g), yield 93%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.12-1.38(m,4H),1.38(s,9H),1.49-1.73(m,4H),2.35-2.41(m,1H),2.83-2.92(m,1H),3.91(s,3H),3.98(s,3H),7.02(s,1H),7.28(s,1H);
13C?NMR(100MHz,D
2O)(ppm):161.3,126.2,125.9,118.1,84.2,55.8,50.9,36.2,35.8,29.6,28.2,26.7,23.5.
Add 7 (0.6g, 1mmol), the 4M hydrochloric acid dioxane aqueous solution (4 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 8 (0.48g), yield 88%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.15-1.29(m,4H),1.56-1.68(m,4H),1.68(d,1H,J=12.8Hz),1.73(d,1H,J=12.8Hz),2.28-2.33(m,1H),2.68-2.78(m,1H),3.95(s,3H),3.98(s,3H),7.13(s,1H),7.39(s,1H);
13C?NMR(100MHz,D
2O)(ppm):129.2,125.8,118.7,66.5,67.1,66.3,33.8,29.3,25.4,23.2.
Embodiment 3
Add 4 (2.5g, 5mmol) in 100 milliliters of there-necked flasks, NaOAc (0.41g, 5mmol) and dehydrated alcohol (25mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 9 (2.05g), yield 96%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.06-1.27(m,4H),1.32(s,9H),1.38-1.59(m,4H),1.85(s,3H),2.31-2.36(m,1H),2.71-2.83(m,1H),3.96(s,3H),4.08(s,3H),7.11(s,1H),7.34(s,1H);
13C?NMR(100MHz,D
2O)(ppm):165.1,125.9,119.6,86.3,53.3,49.6,38.1,35.7,29.6,28.2,26.8,26.3,22.8.
Add 9 (0.6g, 1mmol), the 4M hydrochloric acid dioxane aqueous solution (4 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 10 (0.48g), yield 88%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.21-1.28(m,4H),1.55-1.70(m,4H),1.63(d,1H,J=12.4Hz),1.69(d,1H,J=12.4Hz),1.86(s,3H),2.23-2.31(m,1H),2.68-2.76(m,1H),3.95(s,3H),3.98(s,3H),7.13(s,1H),7.39(s,1H);
13C?NMR(100MHz,D
2O)(ppm):130.5,125.6,120.9,68.1,67.5,64.8,34.6,31.3,29.4,25.9,23.9.
Embodiment 4
Add condensation product 3 (3.58g, 10mmol) in 250 milliliters of there-necked flasks, N-PROPYLE BROMIDE (0.91mL, 10mmol) and toluene (30mL), reflux 8 hours, and TLC detects, and reaction completes.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 11 (4.08g), yield 85%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):1.12-1.44(m,4H),1.42(s,9H),1.45-1.58(m,2H),1.78-1.83(m,2H),2.23-2.38(m,1H),3.01-3.08(m,1H),3.89(s,3H),3.95(s,3H),7.05(s,1H),7.41(s,1H);
13C?NMR(100MHz,D
2O)(ppm):157.1,125.9,125.1,120.5,80.3,56.9,53.8,35.8,34.7,33.4,29.5,25.3,24.2.
16.5.
Add 11 (2.4g, 5mmol), the 4M hydrochloric acid dioxane aqueous solution (4 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 12 (1.75g), yield 92%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.99(t,3H,J=7.2Hz),1.13-1.72(m,6H),1.47-1.62(m,4H),1.58(d,1H,J=12.4Hz),1.65(d,1H,J=12.4Hz),2.09-2.14(m,1H),2.51-2.63(m,1H),3.83(t,2H,J=7.2Hz),3.93(s,3H),7.08(s,1H),7.32(s,1H);
13C?NMR(100MHz,D
2O)(ppm):131.2,124.8,121.5,67.91,67.1,64.6,35.2,34.4,32.5,30.9,29.6,24.8,23.5.
Embodiment 5
Add 11 (4.8g, 5mmol), NaBF in 100 milliliters of there-necked flasks
4(1.1g, 10mmol) and dehydrated alcohol (50mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 13 (2.2g), yield 90%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.92(t,3H,J=7.2Hz),1.21-1.45(m,6H),1.48(s,9H),1.51-1.72(m,4H),2.35-2.41(m,1H),2.89-3.01(m,1H),3.93(t,3H,J=7.2Hz),4.03(s,3H),7.08(s,1H),7.31(s,1H);
13C?NMR(100MHz,D
2O)(ppm):157.9,125.3,125.1,119.2,82.3,55.8,53.1,36.3,33.5,30.8,29.1,26.2,24.7.
Add 13 (2.44g, 5mmol), the 4M hydrochloric acid dioxane aqueous solution (20 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 14 (1.69g), yield 87%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.91(t,3H,J=7.2Hz),1.03-1.18(m,4H),1.48-1.58(m,6H),1.69(d,1H,J=12.8Hz),1.75(d,1H,J=12.8Hz),2.28-2.35(m,1H),2.71-2.75(m,1H),3.86(t,2H,J=7.2Hz),3.91(s,3H),7.08(s,1H),7.31(s,1H);
13CNMR(100MHz,D
2O)(ppm):128.3,124.6,120.3,69.2,66.4,66.1,32.7,31.6,29.5,25.3,24.8.
Embodiment 6
Add 11 (4.8g, 10mmol), LiNTf in 100 milliliters of there-necked flasks
2(2.87g, 10mmol) and dehydrated alcohol (50mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 15 (5.39g), yield 86%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.88(t,3H,J=7.2Hz),1.15-1.36(m,6H),1.45(s,9H),1.53-1.68(m,4H),2.28-2.43(m,1H),3.02-3.09(m,1H),3.96(t,3H,J=7.2Hz),4.08(s,3H),7.11(s,1H),7.31(s,1H);
13C?NMR(100MHz,D
2O)(ppm):158.2,125.5,124.8,120.6,83.5,56.4,53.5,38.2,33.5,31.2,29.5,25.8,25.3.
Add 15 (0.6g, 1mmol), the 4M hydrochloric acid dioxane aqueous solution (5 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains brown oily liquids 16 (0.49g), yield 91%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.93(t,3H,J=7.2Hz),1.05-1.19(m,4H),1.39-1.61(m,6H),1.61(d,1H,J=12.8Hz),1.73(d,1H,J=12.8Hz),2.31-2.36(m,1H),2.63-2.71(m,1H),3.88(t,2H,J=7.2Hz),3.91(s,3H),7.13(s,1H),7.32(s,1H);
13CNMR(100MHz,D
2O)(ppm):129.1,125.2,120.1,68.6,66.5,64.2,32.9,30.9,28.2,24.3,22.9.
Embodiment 7
Add (1R in 250 milliliters of there-necked flasks, the amino hexamethylene t-butyl carbamate of 2R)-2-1 (7.1g, 33mmol), N, N-diisopropylethylamine (3.9g, 33mmol) and chloroform (80mL), 0 ℃ of left and right starts to drip the dichloromethane solution (30mL) of 1-n-propyl-2-SULPHURYL CHLORIDE imidazoles 17 (6g, 33mmol).After dripping end, room temperature reaction 3 hours, TLC point plate reacts completely, and washing, then use dichloromethane extraction, merges organic phase, uses anhydrous sodium sulfate drying, filters, and removes solvent under reduced pressure, and column chromatography for separation obtains white solid 18 (10.0g), yield 85%.Reaction formula is:
Add condensation product 18 (3.58g, 10mmol) in 250 milliliters of there-necked flasks, bromo pentane silane (1.86mL, 30mmol) and toluene (40mL), reflux 8 hours, and TLC detects, and reaction completes.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 19 (4.27g), yield 84%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.93(t,3H,J=7.2Hz),0.96(t,3H,J=7.2Hz),1.08-1.48(m,8H),1.38(s,9H),1.52-1.59(m,2H),1.79-1.82(m,2H),2.33-2.39(m,1H),2.91-3.03(m,1H),3.82-3.88(m,6H),7.12(s,1H),7.29(s,1H);
13C?NMR(100MHz,D
2O)(ppm):157.3,130.2,123.5,118.6,79.2,59.3,56.8,37.9,35.8,35.6,33.6,28.1,26.1,24.3,23.8.
Add 19 (2.54g, 5mmol), the 4M hydrochloric acid dioxane aqueous solution (30 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 20 (1.88g), yield 92%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.89(t,3H,J=7.2Hz),0.92(t,3H,J=7.2Hz),1.08-1.45(m,8H),1.52-1.66(m,6H),1.78(d,1H,J=12.4Hz),1.83(d,1H,J=12.4Hz),2.33-2.41(m,1H),2.71-2.75(m,1H),3.86-3.92(m,4H),7.05(s,1H),7.32(s,1H);
13C?NMR(100MHz,D
2O)(ppm):131.6,125.2,121.2,69.3,68.2,66.5,63.9,35.4,33.7,31.4,29.8,27.5,25.8,24.6,22.1.
Embodiment 8
Add 19 (5.08g, 10mmol), KBF in 100 milliliters of there-necked flasks
6(1.26g, 10mmol) and dehydrated alcohol (60mL), reflux 12 hours.Remove solvent under reduced pressure, with the anhydrous diethyl ether washing, vacuum drying (60 ℃, 5 hours) obtains yellow oily liquid 21 (4.20g), yield 82%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.89(t,3H,J=6.4Hz),0.93(t,3H,J=6.4Hz),1.03-1.48(m,8H),1.42(s,9H),1.53-1.62(m,2H),1.82-1.87(m,2H),2.35-2.45(m,1H),2.95-2.99(m,1H),3.79-3.86(m,6H),7.10(s,1H),7.31(s,1H);
13C?NMR(100MHz,D
2O)(ppm):156.9,131.2,123.8,119.8,78.6,60.3,56.3,38.4,35.5,35.1,32.9,29.3,27.6,25.5,23.9,21.6.
Add 21 (5.13g, 10mmol), the 4M hydrochloric acid dioxane aqueous solution (50 milliliters), stirring at room 12 hours in 100 milliliters of there-necked flasks.Remove solvent under reduced pressure, use the alkali alumina column chromatography, the anhydrous methanol wash-out obtains pale yellow oily liquid body 22 (3.72g), yield 90%.Reaction formula is:
1H?NMR(400MHz,D
2O)(ppm):0.91(t,3H,J=6.4Hz),0.95(t,3H,J=6.4Hz),1.11-1.48(m,8H),1.55-1.68(m,6H),1.82(d,1H,J=12.4Hz),1.85(d,1H,J=12.4Hz),2.33-2.43(m,1H),2.69-2.73(m,1H),3.79-3.88(m,4H),7.03(s,1H),7.33(s,1H);
13C?NMR(100MHz,D
2O)(ppm):130.8,126.3,121.8,70.4,68.1,66.3,62.8,36.4,33.8,31.9,30.5,27.8,24.8,23.7,21.6.
It should be noted that, foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various modifications, be equal to and replace or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (8)
1. a condensation product of take chirality cyclohexanediamine and imidazoles SULPHURYL CHLORIDE, as basic chirality function ionic liquid, is characterized in that, described chirality function ionic liquid has following structural formula I:
Wherein, R
1for the aliphatic chain of C1～C4, R
2for the aliphatic chain of C1～C5, X
--for Br
--, BF
4 --, PF
6 --, NTf
2 -, OAc
-.
2. chirality function ionic liquid as claimed in claim 1, is characterized in that, described R
1the aliphatic chain of C1～C4 be CH
3, CH
3cH
2, CH
3cH
2cH
2, and CH
3cH
2cH
2cH
2.
3. chirality function ionic liquid as claimed in claim 1, is characterized in that, described R
2the aliphatic chain of C1～C5 be CH
3, CH
3cH
2, CH
3cH
2cH
2, CH
3cH
2cH
2cH
2and CH
3cH
2cH
2cH
2cH
2.
4. the preparation method of a chirality function ionic liquid; it is characterized in that; (1R; the amino hexamethylene t-butyl carbamate of 2R)-2-with the imidazoles SULPHURYL CHLORIDE, in temperature of reaction, be to carry out condensation reaction under 0～30 ℃; the condensation product obtained reacts with halogenated alkane, ion exchange reaction and deprotection reaction obtain described chirality function ionic liquid, and its reaction equation is as follows:
Wherein, A is chlorine, bromine and iodine; R
1for the aliphatic chain of C1～C4, R
2for the aliphatic chain of C1～C5, X
--for Br
--, BF
4 --, PF
6 --, NTf
2 --, OAc
--deng.
5. preparation method as claimed in claim 4, is characterized in that, described R
1the aliphatic chain of C1～C4 be CH
3, CH
3cH
2, CH
3cH
2cH
2, and CH
3cH
2cH
2cH
2.
6. preparation method as claimed in claim 4, is characterized in that, described R
2the aliphatic chain of C1～C5 be CH
3, CH
3cH
2, CH
3cH
2cH
2, CH
3cH
2cH
2cH
2and CH
3cH
2cH
2cH
2cH
2.
7. preparation method as claimed in claim 4, is characterized in that, the solvent used in condensation reaction is methylene dichloride, toluene, ethyl acetate, tetrahydrofuran (THF), chloroform and dimethyl sulfoxide (DMSO) etc.
8. preparation method as claimed in claim 4, is characterized in that, the alkali used in condensation reaction is triethylamine, DIPEA and pyridine.
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| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
| CN103073372A (en) * | 2011-10-25 | 2013-05-01 | 中国科学院兰州化学物理研究所 | Method for synthesizing amine compound catalyzed by functionalized ionic liquid |
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| CN102989513A (en) * | 2012-11-28 | 2013-03-27 | 华中农业大学 | Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis |
Non-Patent Citations (2)
| Title |
|---|
| BUKUO NI 等: "Ionic Liquid-Supported (ILS) (S)-Pyrrolidine Sulfonamide, a Recyclable Organocatalyst for the Highly Enantioselective Michael Addition to Nitroolefins", 《ORGANIC LETTERS》 * |
| EMMY M.OMAR 等: "Ionic liquid-supported (ILS) (S)-pyrrolidine sulfonamide for asymmetric Michael addition reactions of aldehydes with nitroolefins", 《LETTERS IN ORGANIC CHEMISTRY》 * |
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