CN103073454A - Synthetic method for beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone - Google Patents
Synthetic method for beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone Download PDFInfo
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- 0 C[n]1c[n+](*)cc1 Chemical compound C[n]1c[n+](*)cc1 0.000 description 2
- UNNWXMYWHXKEBT-UHFFFAOYSA-N CCC(CC(C)NC(OCC)=O)=O Chemical compound CCC(CC(C)NC(OCC)=O)=O UNNWXMYWHXKEBT-UHFFFAOYSA-N 0.000 description 1
- DGZDXQBBJXMZCZ-UHFFFAOYSA-N CCOC(NC(CCC1)CC1=O)=O Chemical compound CCOC(NC(CCC1)CC1=O)=O DGZDXQBBJXMZCZ-UHFFFAOYSA-N 0.000 description 1
- IJNQJQRKLLCLMC-UHFFFAOYSA-N CNc1cc2ccccc2cc1 Chemical compound CNc1cc2ccccc2cc1 IJNQJQRKLLCLMC-UHFFFAOYSA-N 0.000 description 1
- SPGPGBWICPNRSN-UHFFFAOYSA-O I[n]1c[nH+]cc1 Chemical compound I[n]1c[nH+]cc1 SPGPGBWICPNRSN-UHFFFAOYSA-O 0.000 description 1
- JHZQJNXJTGSMNE-UHFFFAOYSA-N O=C(CCC1)CC1Nc1cc2ccccc2cc1 Chemical compound O=C(CCC1)CC1Nc1cc2ccccc2cc1 JHZQJNXJTGSMNE-UHFFFAOYSA-N 0.000 description 1
- IHGXZHQOQHMWLZ-UHFFFAOYSA-N O=C(CCC1)CC1Sc(cc1)ccc1Cl Chemical compound O=C(CCC1)CC1Sc(cc1)ccc1Cl IHGXZHQOQHMWLZ-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N Sc(cc1)ccc1Cl Chemical compound Sc(cc1)ccc1Cl VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N c1ccncc1 Chemical compound c1ccncc1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a synthetic method for a beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone. In the method, ionic liquid is used as a catalyst, and aza-Michael, sulfa-Michael and oxa-Michael reactions of electron-deficient ketene and a nucleophilic reagent are carried out at room temperature so as to synthesize corresponding compounds. According to the invention, usage amount of the catalyst is small, and the catalyst has the advantages of high catalytic activity, good stability, low corrosivity, cyclical usability, good selectivity of products, simple operation and strong controllability; a substrate has a wide application scope, and good yield is obtained in addition of alcohol compounds with low reaction activity; the reactions are mild; reaction products and the catalyst can be easily separated, and the catalyst can be cyclically used.
Description
Technical field
The invention belongs to the synthetic field of beta-amino carbonyl compound, β-sulfydryl ketone, β-ketonic ether, be specifically related to a kind of ionic liquid-catalyzed α that utilizes, the method for the synthetic beta-amino carbonyl compound of hetero-Michael reaction of beta-unsaturated carbonyl compound and nucleophilic reagent, β-sulfydryl ketone, β-ketonic ether.
Background technology
The compounds such as the beta-amino carbonyl compound that the chemical bonds such as C-N, the C-S that makes up by the hetero-Michael addition, C-O form, β-sulfydryl ketone, β-ketonic ether, be important organic structure unit, in organic synthesis and pharmaceutical chemistry, play an important role.
The beta-amino carbonyl compound can be used for synthetic 1, the organic compounds containing nitrogens such as 3-amino alcohol, beta-amino acids, beta-amino ketones, beta-lactam, and then can synthesize many medicine and natural products with life and physiologically active, be important organic synthesis intermediate.β-sulfhydryl compound is present in the life entity and animal and plant body alive in a large number, is that vital movement institute is indispensable; The compound that is widely used in synthetic bioactive, for example: can syncillin, cynnematin, sulfa drug, vitamins B
1Etc. important medicine; In addition, the alkylthio in the β-carbonyl sulfide of formation is at Cu
+Or easily be divested under the condition of oxygenant existence, therefore being protection α, the carbon-carbon double bond in the beta-unsaturated carbonyl compound provides a kind of method.β-ketonic ether is the organic synthesis intermediate with extensive use, can be used for synthesis of hydroxy carbonyl compound or amino alcohol etc., and these two is structure fragment common in the natural product.Along with deepening continuously of oxa-Michael research, this reaction is used to the compound that contains pyranoid ring or furan ring structure fragment of synthesizing new more and more, have bioactive natural product especially for synthesizing, such as: the natural product with HIV (human immunodeficiency virus)-resistant activity adjoins the type coumarin kind compound (+) of muttering-Inophyllum B and (+)-Calanolide A etc.
Nucleophilic reagent (amino formate, nitrogen-containing heterocycle compound, phenyl amines, thiophenol or mercaptan, Fatty Alcohol(C12-C14 and C12-C18) etc.) and α, beta-unsaturated carbonyl compound, reaction generates corresponding beta-amino carbonyl compound, β-sulfydryl ketone, β-ketonic ether under an acidic catalyst effect, and this reaction catalyst system commonly used has: Lewis acid reaches
Acid, the phosphorus part, azepine copper Cabbeen etc., for example: [Pd (CH
3CN)
2Cl
2] (Org.Lett.2001,3,25), Cu (OTf)
2(Tetrahedron Lett.2002,43,3891), VO (OTf)
2(Org.Lett.2007,9,5195), Bi (NO
3)
3(J.Org.Chem.2003,68,2109), RhCl
33H
2O (Org.Lett 2002,4,1319), RuCl
3(Org.Biomol.Chem.2006,4,393), Tf
2NH (Chem.Eur.J.2004,10,484), PMe3 (J.Am.Chem.Soc.2003,125,8696), (IPr) Cu (NHPh) (Organometallics 2007,26,1483) etc., although these methods have obtained some successes, wherein there is very large defective: such as long reaction time, severe reaction conditions, the reaction solvent consumption is large, and in reaction, also used some poisonous solvents, such as acetonitrile etc., this has not only brought harm to human body, waste liquid is returned environment and has been brought serious pollution simultaneously, because catalyzer also has very strong corrodibility, can not recycle, so its cost is higher aborning in addition.In view of above-mentioned situation, urgent need will be developed a kind of energy Reaction time shorten, improve reaction efficiency, human body is safe from harm, environment amenable environmental protection catalyzer.
The acid functionalization ionic liquid is with the advantage such as its unique physico-chemical property, chemical stability, low volatility, high resolution and molecular structure be adjustable, successfully apply in the organic catalytic reaction, both shown the advantage of homogeneous reaction, can realize multi-phase separation again, simple to operate, can repeatedly recycle, and the activity of catalyzer does not significantly reduce.Therefore it is necessary to utilize the ionic liquid-catalyzed hetero-Michael addition reaction of acid functionalization to synthesize beta-amino carbonyl compound, β-sulfydryl ketone, β-ketonic ether, although but patent CN200810167605.4 utilizes ionic liquid to come catalysis aza-Michael addition reaction as catalyzer, but be only limited to the stronger amine of catalysis nucleophilicity, do not relate to nucleophilicity weak aminocarboxylic acid ester compound and sulfa-Michael, oxa-Michael.And among the present invention, addition reaction all shows preferably catalytic activity to the acid functionalization ionic liquid to hetero-Michael (aza-Michael, sulfa-Michael, oxa-Michael), and the substrate suitability is more extensive.
Summary of the invention
The defective such as the object of the invention is to overcome that the catalytic erosion that exists in the prior art is strong, severe reaction conditions, long reaction time, side reaction are many, under relatively mild condition, provide a kind of ionic liquid-catalyzed α, more effective, the more economical and eco-friendly method of the synthetic beta-amino carbonyl compound of hetero-Michael reaction of beta-unsaturated carbonyl compound and nucleophilic reagent, β-sulfydryl ketone, β-ketonic ether.
Chemical equation of the present invention
The present invention utilizes ionic liquid-catalyzed α, the method for the synthetic beta-amino carbonyl compound of hetero-Michael reaction of beta-unsaturated carbonyl compound and nucleophilic reagent, β-sulfydryl ketone, β-ketonic ether.
A kind of beta-amino carbonyl compound, β-sulfydryl ketone, the synthetic method of β-ketonic ether, it is characterized in that: use amino formate, nitrogen-containing heterocycle compound, phenyl amines, thiophenol or benzenethiol, Fatty Alcohol(C12-C14 and C12-C18) nucleophilic reagent and α, beta-unsaturated carbonyl compound is as reactant, with functionalized ion liquid as catalyzer, wherein the cationic moiety of functionalized ion liquid is selected from glyoxaline cation or pyridylium, anionicsite is selected from the trifluoromethanesulfonic acid root, bisulfate ion, the tosic acid root, tetrafluoroborate, hexafluoro-phosphate radical or dihydrogen phosphate, under 20-30 ℃, reaction times 1～48h, the hetero-Michael addition reaction generates corresponding beta-amino carbonyl compound, β-sulfydryl ketone, β-ketonic ether compound.
Catalyzer is a kind of in the following description:
R wherein
1, R
2, R
3Group represents respectively C
1～C
20With interior fat group, comprise methyl, ethyl or butyl, X
-Represent tosic acid root (OTs
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6 -), bisulfate ion (HSO
4 -) or dihydrogen phosphate (H
2PO
4 -), n represents 1～6 integer.
In aforesaid method, nitrogen-containing heterocycle compound is selected from urethanum, benzyl carbamate, t-butyl carbamate, butyl carbamate, oxazolinone, imidazoles, benzoglyoxaline, pyrazoles, 1,2,4-triazole, benzotriazole or benzo tetrazole.
In aforesaid method, thiophenol or mercaptan are selected from thiophenol, 4-methylbenzene phenyl-sulfhydrate, 4-chlorothio-phenol, 2-thionaphthol, 4-methoxybenzenethiol, 2-methylbenzene phenyl-sulfhydrate, beneze methane thiol or hexylmercaptan.
In aforesaid method, Fatty Alcohol(C12-C14 and C12-C18) is selected from methyl alcohol, ethanol, chloroethanol, Virahol or phenylcarbinol.
In aforesaid method, α, beta-unsaturated carbonyl compound are selected from 2-tetrahydrobenzene-1-ketone, 3-methyl-2-tetrahydrobenzene-1-ketone, 2-cyclopentene-1-one, 3-methyl-2-cyclopentene-1-one, 3-amylene-2-ketone, methylene acetone, 4-methyl-3-amylene-2-ketone, 4-hexene-3-one, 1-phenyl-2-butylene-1-ketone, N-phenyl butylene imide, methyl acrylate or vinyl cyanide.
In aforesaid method, nucleophilic reagent and α, the mol ratio of beta-unsaturated carbonyl compound is 1: 1～4: 1.
The present invention has the following advantages: catalyst levels is few, and catalytic activity is high; Catalyst stability is good; Catalytic erosion is low, and is simple to operate, reaction temperature and; The wide application range of substrates of catalyst system, good product selectivity; Reaction product and catalyzer are easily separated, and catalyzer can be realized recycling.
In a word, catalytic erosion of the present invention is low, catalytic activity is high and can be recycled, and good product selectivity is Isosorbide-5-Nitrae-conjugate addition product, the easy easy operation of reaction process, and controllability is strong.
Embodiment
Being expressed as follows of catalyzer:
R wherein
1, R
2, R
3Group represents respectively C
1～C
20With interior fat group, comprise methyl, ethyl or butyl, X
-Represent tosic acid root (OTs
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6 -), bisulfate ion (HSO
4 -) or dihydrogen phosphate (H
2PO
4 -),, n represents 1～6 integer.
Being abbreviated as of used several ionic liquids wherein:
Hetero-Michael reaction product preparation process:
In the reaction flask of magnetic agitation is housed, add successively nucleophilic reagent (nitrogen-containing heterocycle compound, thiophenol or benzenethiol, Fatty Alcohol(C12-C14 and C12-C18)), α, beta-unsaturated carbonyl compound and ionic liquid.Wherein nucleophilic reagent and α, the mol ratio of beta-unsaturated carbonyl compound is 1: 1～4: 1, the consumption of catalyzer is 1～100mol%, react 1～48h under the room temperature, thin-layer chromatography is followed the tracks of reaction process, uses the ethyl acetate extraction reaction solution, column chromatography for separation obtains sterling, carry out the next batch reaction behind 80 ℃ of vacuum-drying 24h of ionic liquid, ionic liquid is reused 5 times, has no reaction yield and obviously descends.
Embodiment 1:
Under the room temperature, with cyclonene (0.5mmol, 49.0mg) and urethanum (0.6mmol, 53.4mg) and [Hmim] OTs (1mL), place dry reaction flask, reaction 24h.Reaction is carried out qualitative analysis by Hewlett-Packard 6890/5973GC-MS and NMR after finishing.Agilent 6820 gas chromatographs carry out quantitative analysis.The productive rate of 3-urethanum basic ring hexanone is 75%.
1H?NMR(400MHz，CDCl
3)δ＝1.24(t，J＝6.8Hz，3H)，1.67-1.77(m，2H)，1.99-2.03(m，1H)，2.08-2.18(m，1H)，2.27-2.40(m，3H)，2.27-2.40(m，1H)，2.70(dd，J＝4.8，4.8Hz，1H)，3.97(s，1H)，4.10(t，J＝2.0Hz，2H)，5.09(d，J＝7.2Hz，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝14.6，22.0，31.2，40.8，48.0，50.1，60.8，155.7，209.0.
Embodiment 2:
With example 1, catalyst system therefor is [Hmim] HSO
4, the productive rate of 3-urethanum basic ring hexanone is 70%.
Embodiment 3:
With example 1, catalyst system therefor is [Hmim] BF
4, the productive rate of 3-urethanum basic ring hexanone is 71%.
Embodiment 4:
With example 1, catalyst system therefor is [Bmim] H
2PO
4, the productive rate of 3-urethanum basic ring hexanone is 77%.
Embodiment 5:
With example 1, catalyst system therefor is [Bmim] OTs, and the productive rate of 3-urethanum basic ring hexanone is 47%.
Embodiment 6:
With example 1, catalyst system therefor is [Sbmim] OTf, and the productive rate of 3-urethanum basic ring hexanone is 79%.
Embodiment 7:
With example 1, catalyst system therefor is [Bmim] OTf, and the productive rate of 3-urethanum basic ring hexanone is 59%.
Embodiment 8:
With example 1, catalyst system therefor is [Sbmim] HSO
4, the productive rate of 3-urethanum basic ring hexanone is 62%.
Embodiment 9:
With example 1, catalyst system therefor is [Bmim] HSO
4, the productive rate of 3-urethanum basic ring hexanone is 53%.
Embodiment 10:
With example 1, catalyst system therefor is PyHSO
4, the productive rate of 3-urethanum basic ring hexanone is 50%.
Embodiment 11:
With example 1, catalyst system therefor is [Hmim] OTs (10mol%, 12.7mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 54.6mg, productive rate is 59% to column chromatography for separation after reaction finishes.
Embodiment 12:
With example 1, catalyst system therefor is [Hmim] OTs (20mol%, 25.4mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 61.1mg, productive rate is 66% to column chromatography for separation after reaction finishes.
Embodiment 13:
With example 1, catalyst system therefor is [Hmim] OTs (30mol%, 38.1mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 75.9 mg, productive rate is 82% to column chromatography for separation after reaction finishes.
Embodiment 14:
With example 1, catalyst system therefor is [Hmim] OTs (40mol%, 50.8mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 76.8mg, productive rate is 83% to column chromatography for separation after reaction finishes.
Embodiment 15:
With example 1, catalyst system therefor is [Hmim] OTs (50mol%, 63.5mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 78.6mg, productive rate is 85% to column chromatography for separation after reaction finishes.
Embodiment 16:
With example 1, catalyst system therefor is [Hmim] OTs (80mol%, 101.6mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 79.6mg, productive rate is 86% to column chromatography for separation after reaction finishes.
Embodiment 17:
With example 1, catalyst system therefor is [Hmim] OTs (100mol%, 127.0mg), reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 80.1mg, productive rate is 87% to column chromatography for separation after reaction finishes.
Embodiment 18:
Under the room temperature, with cyclonene (0.5mmol, 49.0mg) and benzyl carbamate (0.6mmol, 90.6mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 86.5mg, productive rate is 70% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.71-1.62(m，2H)，2.12-1.96(m，2H)，2.40-2.25(m，3H)，2.74-2.69(m，1H)，4.08-3.90(m，1H)，4.80(s，1H)，5.10-5.09(m，2H)，7.38-7.32(m，5H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.9，31.1，40.8，47.9，50.2，66.8，128.1，128.2，128.6，136.2，155.2，208.5.
Embodiment 19:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and urethanum (0.6mmol, 53.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 16h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 84.8mg, productive rate is 98% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.16(t，J＝6.4Hz，6H)，2.09(s，3H)，2.53(dd，J＝6.4，6.4Hz，1H)，2.65(dd，J＝5.2，5.2Hz，1H)，3.98-4.02(m，3H)，5.09(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝13.6，19.6，29.5，42.6，48.3，59.6，154.9，206.6.
Embodiment 20:
Under the room temperature, with 3-methylene acetone (0.5mmol, 42mg) and urethanum (0.6mmol, 53.4mg) and [Hmim] OTs (30mol%, 38.1mg)), place dry reaction flask, reaction 16h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 75.5mg, productive rate is 95% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.06(t，J＝7.6Hz，3H)，1.22(t，J＝7.2Hz，3H)，2.44(q，J＝14.4Hz，2H)，2.66(t，J＝5.6Hz，2H)，3.41(q，J＝11.2Hz，2H)，4.08(q，J＝14.0Hz，2H)，5.21(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝7.6，14.5，35.5，36.1，41.9，60.6，156.6，210.8.
Embodiment 21:
Under the room temperature, with 4-hexene-3-one (0.5mmol, 49mg) and urethanum (0.6mmol, 53.4mg) and [Hmim] OTs (30mol%, 38.1mg)), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 80.4mg, productive rate is 86% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝0.97(t，J＝7.2Hz，3H)，1.14-1.17(m，6H)，2.37(q，J＝14.4Hz，2H)，2.51(dd，J＝5.2，5.2Hz，1H)，2.63(dd，J＝4.8，4.8Hz，1H)，3.96-4.01(m，3H)，5.16(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝6.6，13.6，19.6，35.5，42.7，59.6，154.9，209.3.
Embodiment 22:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73mg) and urethanum (0.6mmol, 53.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 65.8mg, productive rate is 56% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.23(t，J＝7.2Hz，3H)，1.30(d，J＝6.8Hz，3H)，3.06(dd，J＝6.4，6.8Hz，1H)，3.38(d，J＝14.0Hz，1H)，4.10(q，J＝14.0Hz，2H)，4.19-4.26(m，1H)，5.21(s，1H)，7.47(t，J＝7.2Hz，2H)，7.58(t，J＝7.6Hz，1H)，7.97(d，J＝7.2Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝14.6，20.4，44.2，44.3，60.7，128.1，128.7，133.3，136.9，155.9，198.8.
Embodiment 23:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and imidazoles (0.6mmol, 40.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.Column chromatography for separation after reaction finishes (adopts silicagel column, eluent: CH
2Cl
2/ CH
3OH=20/1), obtain sterling 49.4mg, productive rate is 65%.
1H?NMR(400MHz，CDCl
3)δ＝1.49(d，J＝6.8Hz，3H)，2.09(s，3H)，2.80(dd，J＝6.4，6.4Hz，1H)，2.93(dd，J＝6.8，6.8Hz，1H)，4.70-4.79(m，1H)，6.93(s，1H)，7.03(s，1H)，7.53(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.7，30.5，48.7，51.0，116.6，129.4，135.8，204.8.
Embodiment 24:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and pyrazoles (0.6mmol, 40.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 57.8mg, productive rate is 76% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)：δ＝1.52(d，J＝6.8Hz，3H)，2.07(s，3H)，2.81(dd，J＝6.0，17.2Hz，1H)，3.25(dd，J＝7.2，17.2Hz，1H)，4.88-4.80(m，1H)，?6.20(t，J＝2.4Hz，1H)，7.43(d，J＝2.0Hz，1H)，7.53(d，J＝1.6Hz，1H).
13C?NMR(100MHz，CDCl
3)：δ＝21.2，30.5，49.8，53.2，104.8，139.3，206.0.
Embodiment 25:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and benzoglyoxaline (0.6mmol, 70.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.Column chromatography for separation after reaction finishes (adopts silicagel column, eluent: CH
2Cl
2/ CH
3OH=30/1), obtain sterling 79.8mg, productive rate is 79%.
1H?NMR(400MHz，CDCl
3)δ＝1.66(d，J＝7.2Hz，3H)，2.12(s，3H)，2.98(dd，J＝7.2，7.2Hz，1H)，3.16(dd，J＝5.6，6.0Hz，1H)，5.01-5.10(m，1H)，7.27-7.32(m，2H)，7.46(d，J＝6.8Hz，1H)，7.81(d，J＝6.4Hz，1H)，7.99(s，1H).
13CNMR(100.8MHz，CDCl
3)δ＝20.6，30.5，47.5，49.4，110.2，122.2，122.8，132.7，141.2，144.0，204.8.
Embodiment 26:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and benzotriazole (0.6mmol, 71.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 3h.Column chromatography for separation after reaction finishes (adopts silicagel column, eluent: CH
2Cl
2/ CH
3OH=50/1), obtain sterling 93.4mg, productive rate is 92%.
1H?NMR(400MHz，CDCl
3)δ＝1.66(d，J＝7.2Hz，3H)，2.12(s，3H)，2.98(dd，J＝7.2，7.2Hz，1H)，3.16(dd，J＝5.6，6.0Hz，1H)，5.01-5.10(m，1H)，7.27-7.32(m，2H)，7.46(d，J＝6.8Hz，1H)，7.81(d，J＝6.4Hz，1H)，7.99(s，1H).
13CNMR(100MHz，CDCl
3)δ＝20.6，30.5，47.5，49.4，110.2，122.2，122.8，132.7，141.2，144.0，204.8.
Embodiment 27:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and 5-phenyl tetrazole (0.6mmol, 87.6mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 1h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 109.3mg, productive rate is 95% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.59(d，J＝6.8Hz，3H)，2.13(s，3H)，2.96(dd，J＝6.4，6.4Hz，1H)，3.38(dd，J＝6.8，7.2Hz，1H)，5.34-5.42(m，1H)，7.36-7.41(m，3H)，8.05(dd，J＝2.0，2.4Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝19.8，29.3，47.3，54.9，125.8，126.4，127.8，129.2，163.8，203.1.
Embodiment 28:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and thiophenol (0.6mmol, 66.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 18h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 99.9mg, productive rate is 97% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.67-1.79(m，2H)，2.11-2.18(m，2H)，2.30-2.41(m，3H)，2.68(dd，J＝4.4，4.4Hz，1H)，3.39-3.46(m，1H)，7.28-7.34(m，3H)，7.42(dd，J＝1.6，2.0Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝24.0，31.2，40.8，46.1，47.7，127.8，129.0，133.0，133.2，208.7
Embodiment 29:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 4-methylbenzene phenyl-sulfhydrate (0.6mmol, 74.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 94.6mg, productive rate is 86% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.57-1.67(m，2H)，2.01-2.09(m，2H)，2.19-2.29(m，6H)，2.57(dd，J＝4.4，4.4Hz，1H)，3.22-3.29(m，1H)，7.04(d，J＝8.0Hz，2H)，7.05(d，J＝8.0Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝20.1，23.0，30.2，39.8，45.4，46.7，128.1，128.8，132.9，137.1，207.8.
Embodiment 30:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and phenyl thiomethyl alcohol (0.6mmol, 74.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 75.9mg, productive rate is 69% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.62-1.74(m，2H)，2.06-2.10(m，2H)，2.29-2.34(m，2H)，2.37(t，J＝4.0Hz，1H)，2.66(dd，J＝4.4，4.8Hz，1H)，2.89-2.96(m，1H)，3.75(d，J＝2.0Hz，1H)，7.22-7.25(m，1H)，7.30(d，J＝4.4Hz，4H).
13C?NMR(100.8MHz，CDCl
3)δ＝24.0，31.2，34.8，40.8，41.8，47.7，127.0，128.5，128.6，137.8，208.5.
Embodiment 31:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 2-thionaphthol (0.6mmol, 96.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 105.0mg, productive rate is 82% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.64-1.81(m，2H)，2.08-2.20(m，2H)，2.24-2.44(m，3H)，2.69-2.74(m，1H)，3.49-3.56(m，1H)，7.44-7.50(m，3H)，7.75-7.81(m，3H)，7.89(d，1H).
13C?NMR(100MHz，CDCl
3)δ＝30.3，39.8，45.1，46.7，125.4，125.6，126.4，126.7，127.6，129.2，129.4，131.1，131.5，132.6，207.6.
Embodiment 32:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 4-chlorothio-phenol (0.6mmol, 86.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 28h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 111.6 mg, productive rate is 93% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.63-1.78(m，2H)，2.12-2.17(m，2H)，2.31-2.39(m，3H)，2.67(dd，J＝4.4，4.4Hz，1H)，3.37-3.44(m，1H)，7.29(d，J＝8.4Hz，2H)，7.36(d，J＝8.4Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝24.0，31.1，40.8，46.4，47.6，129.3，131.5，134.1，134.6，208.4.
Embodiment 33:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 4-methoxybenzenethiol (0.6mmol, 84.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 108.6mg, productive rate is 92% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.64-1.69(m，2H)，2.09-2.15(m，2H)，2，24-2.34(m，3H)，2.61(dd，J＝4.4，4.4Hz，1H)，3.19-3.25(m，1H)，3.78(s，3H)，6.84(d，J＝8.8Hz，2H)，7.38(d，J＝8.8Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝24.0，31.1，40.7，46.9，47.7，55.2，114.5，122.8，136.4，159.9，209.0.
Embodiment 34:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 2-methylbenzene phenyl-sulfhydrate (0.6mmol, 74.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 32h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 102.3mg, productive rate is 93% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.69-1.82(m，2H)，2.11-2.17(m，2H)，2.32-2.40(m，3H)，2.43(s，3H)，2.68(dd，J＝4.4，4.8Hz，1H)，3.39-3.45(m，1H)，7.14-7.23(m，3H)，7.39(dd，J＝1.6，1.6Hz，1H).
13C?NMR?(100.8MHz，CDCl
3)δ＝20.9，24.1，31.3，40.9，45.6，47.7，126.5，127.7，130.5，132.6，133.2，140.5，208.7.
Embodiment 35:
Under the room temperature, with 1-hexamethylene-2-ketone (0.5mmol, 49.0mg) and 1-hexylmercaptan (0.6mmol, 70.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 65.3mg, productive rate is 61% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝0.84(t，J＝6.8Hz，3H)，1.21-1.27(m，4H)，1.29-1.37(m，2H)，1.49-1.56(m，2H)，1.64-1.72(m，2H)，2.07-2.14(m，2H)，2.27-2.37(m，3H)，2.50(t，J＝7.2Hz，2H)，2.66(dd，J＝4.4，4.4Hz，1H)，2.99-3.04(m，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝13.9，22.4，24.2，28.5，29.6，30.4，31.3，31.6，40.9，42.7，48.1，208.8.
Embodiment 36:
Under the room temperature, with N-phenyl succimide (0.5mmol, 49.0mg) and thiophenol (0.6mmol, 66.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 128.8mg, productive rate is 91% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.92-2.87(m，1H)，3.56-3.29(m，1H)，4.15-4.12(m，1H)，7.35(d，J＝6.8Hz，2H)，7.43-7.34(m，6H)，7.77(d，J＝6.8Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝36.4，44.1，126.3，128.8，129.1，129.5，129.7，131.5，135.1，173.5，174.5.
Embodiment 37:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) and 4-methoxybenzenethiol (0.6mmol, 84.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 4h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 110.9mg, productive rate is 99% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.24(d，J＝6.8Hz，3H)，2.12(s，3H)，2.51(dd，J＝8.4，8.4Hz，1H)，2.71(dd，J＝5.2，5.6Hz，1H)，3.46-3.55?(m，1H)，3.80(m，3H)，6.85(d，J＝8.4Hz，2H)，7.39(d，J＝8.8Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.0，30.5，39.4，50.4，55.3，114.5，124.0，136.0，159.7，206.7.
Embodiment 38:
Under the room temperature, with benzylidene-acetone (0.5mmol, 73mg) and 4-methoxybenzenethiol (0.6mmol, 84.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 6h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 111.5mg, productive rate is 78% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.07(s，3H)，3.03(dd，J＝2.0，2.8Hz，2H)，3.77(s，3H)，4.53(t，J＝7.6Hz，1H)，6.76(d，J＝8.8Hz，2H)，7.17-7.25(m，7H).
13C?NMR(100.8MHz，CDCl
3)δ＝30.7，49.1，55.3，114.3，124.0，127.3，127.7，128.4，136.3，141.2，159.9，205.7.
Embodiment 39:
Under the room temperature, with methyl acrylate (0.5mmol, 43mg) and thiophenol (0.6mmol, 66.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 6h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 98.0mg, productive rate is 81% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝3.14(d，J＝6.4Hz，1H)，3.27(dd，J＝5.6，5.6Hz，1H)，3.39(dd，J＝4.0，4.0Hz，1H)，3.61(s，3H)，4.39-4.43(m，1H)，7.20-7.24(m，1H)，7.28-7.31(m，2H)，7.43(d，J＝7.2Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝39.1，52.5，69.3，126.9，129.0，130.7，134.8，173.1.
Embodiment 40:
Under the room temperature, with vinyl cyanide (0.5mmol, 26.5mg) and thiophenol (0.6mmol, 66.0mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 4h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 72.6mg, productive rate is 89% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.58(t，J＝7.2Hz，2H)，3.12(t，J＝7.2Hz，2H)，7.28-7.36(m，3H)，7.42(dd，J＝0.8，0.8Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝18.1，30.1，117.9，127.6，129.3，131.3，133.1.
Embodiment 41:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42.0mg) and anhydrous methanol (2.0mmol, 64.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 12h.(adopt silicagel column, eluent: sherwood oil/acetoacetic ester=5/1), obtain sterling 49.3mg, productive rate is 85% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)：δ＝1.15(d，J＝6.4Hz，3H)，2.15(s，3H)，2.41(dd，J＝5.6，16Hz，1H)，2.70(dd，J＝7.2，16Hz，1H)，3.29(s，3H)，3.73-3.81(m，1H).
13C?NMR(100MHz，CDCl
3)：δ19.1，30.9，50.5，56.2，73.1，207.4.
Embodiment 42:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42.0mg) and dehydrated alcohol (2.0mmol, 92.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 12h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 49.4mg, productive rate is 76% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)：δ＝1.12-1.15(m，6H)，2.15(s，3H)，3.34-3.41(m，1H)，3.49-3.57(m，1H)，3.29(s，3H)，3.82-3.89(m，1H).
13C?NMR(100MHz，CDCl
3)：δ＝15.4，19.9，31.0，50.7，63.9，71.5，207.6.
Embodiment 43:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42.0mg) and chloroethanol (2.0mmol, 160.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 12h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 50.0mg, productive rate is 61% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.15(d，J＝5.88Hz，3H)，2.13(s，3H)，2.40(dd，J＝5.2，16.4Hz，1H)，2.71(dd，J＝7.6，16Hz，1H)，3.51-3.61(m，3H)，?3.68-3.74(m，1H)，3.87-3.95(m，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝19.7，31.1，43.1，50.5，68.9，72.3，207.2.
Embodiment 44:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42.0mg) and Virahol (2.0mmol, 120.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 12h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain sterling 47.5mg, productive rate is 66% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)：δ＝1.07-1.15(m，9H)，2.16(s，3H)，2.39(dd，J＝5.6，15.6Hz，1H)，2.68(dd，J＝7.2，15.2Hz，1H)，3.60-3.66(m，1H)，3.90-3.98(m，1H).
13C?NMR(100MHz，CDCl
3)：δ20.9，22.2，23.2，31.3，51.2，69.2，69.4，207.9.
Embodiment 45:
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42.0mg) and phenylcarbinol (2.0mmol, 216.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 48h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=10/1), obtain sterling 57.6mg, productive rate is 60% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.22(d，J＝6.0Hz，3H)，2.13(s，3H)，2.46(dd，J＝5.6，16.0Hz，1H)，2.77(dd，J＝7.2，16.0Hz，1H)，3.98-4.06(m，1H)，4.43(d，J＝11.6Hz，1H)，4.55(d，J＝11.6Hz，1H)，7.24-7.28(m，1H)，7.30-7.34(m，4H).
13C?NMR(100.8MHz，CDCl
3)δ＝19.8，31.0，50.8，65.1，70.8，71.6，127.7，128.4，138.5，207.5.
Embodiment 46:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and anhydrous methanol (2.0mmol, 64.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 48h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 69.4mg, productive rate is 78% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝1.26(d，J＝6.4Hz，3H)，2.92(dd，J＝6.0，6.0Hz，1H)，3.34(s，3H)，3.34(dd，J＝6.4，6.8Hz，1H)，3.96-4.04(m，1H)，7.46(t，J＝7.6Hz，2H)，7.56(t，J＝7.6Hz，1H)，7.97(d，J＝7.2Hz，2H).?
13C?NMR(100.8MHz，CDCl
3)δ＝19.5，45.4，56.4，73.5，128.1，128.5，133.0，137.2，198.6.
Embodiment 47:
Under the room temperature, with N-phenyl succimide (0.5mmol, 49.0mg) and anhydrous methanol (2.0mmol, 64.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 48h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain sterling 23.6mg, productive rate is 23% to column chromatography for separation after reaction finishes.(
1H?NMR(400MHz，CDCl
3)：δ＝3.95(s，3H)，6.22(d，J＝13.2Hz，1H)，6.44(d，J＝13.6Hz，1H)，7.13(t，J＝7.6Hz，1H)，7.34(t，J＝8.4Hz，2H)，7.67(d，J＝7.6Hz，2H)，10.83(s，1H).
13C?NMR(100MHz，CDCl
3)：δ＝52.8，120.1，124.6，124.9，129.0，137.8，140.3，161.4，167.2.
Embodiment 48:
Under 60 ℃, with N-phenyl succimide (0.5mmol, 49.0mg) and anhydrous methanol (2.0mmol, 64.0mg) and [Hmim] OTs (50mol%, 63.5mg), place dry reaction flask, reaction 12h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=2/1), obtain sterling 66.6mg, productive rate is 65% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)：δ＝3.95(s，3H)，6.22(d，J＝13.2Hz，1H)，6.44(d，J＝13.6Hz，1H)，7.13(t，J＝7.6Hz，1H)，7.34(t，J＝8.4Hz，2H)，7.67(d，J＝7.6Hz，2H)，10.83(s，1H).
13C?NMR(100MHz，CDCl
3)：δ＝52.8，120.1，124.6，124.9，129.0，137.8，140.3，161.4，167.2.
Embodiment 49:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and oxazoline ketone (0.6mmol, 90.6mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 50.1mg, productive rate is 43% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.33(d，J＝6.8Hz，3H)，3.14(dd，J＝6.8，6.4Hz，1H)，3.45(dd，J＝7.2，7.2Hz，1H)，3.58-3.67(m，1H)，4.28(t，J＝8.0Hz，2H)，4.32-4.39(m，1H)，7.46(t，J＝7.6Hz，2H)，7.56(t，J＝7.6Hz，1H)，7.95(t，J＝7.6Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝17.7，42.3，42.5，62.0，128.1，128.7，133.4，136.4，157.5，197.7.
Embodiment 50:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and imidazoles (0.6mmol, 40.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 55.6mg, productive rate is 52% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝3.20(d，J＝6.8Hz，3H)，3.33(dd，J＝6.8，6.4Hz，1H)，3.48(dd，J＝6.4，6.4Hz，1H)，4.96-5.00(m，1H)，7.02(d，J＝8.8Hz，2H)，7.45-7.47(m，2H)，7.55-7.57(m，1H)，7.61(s，1H)，7.88(d，J＝7.2Hz，2H).?
13C?NMR(100.8MHz，CDCl
3)δ＝21.7，46.2，48.9，116.6，127.8，128.6，129.2，133.5，135.8，136.1，196.1.
Embodiment 51:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and pyrazoles (0.6mmol, 40.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 58.9 mg, productive rate is 55% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.61(d，J＝6.8Hz，1H)，3.32(dd，J＝6.0，6.4Hz，1H)，3.78(dd，J＝6.8，6.4Hz，1H)，5.01-5.10(m，1H)，6.17(t，J＝2.0Hz，1H)，7.42(t，J＝7.6Hz，2H)，7.48-7.50(m，2H)，7.53(t，J＝7.6Hz，1H)，7.91(d，J＝7.2Hz，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.3，45.2，53.4，104.6，128.0，128.5，133.3，136.5，139.3，197.3.
Embodiment 52:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and benzoglyoxaline (0.6mmol, 70.8mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/2), obtain sterling 80.5mg, productive rate is 61% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.76(d，J＝6.8Hz，3H)，3.52(dd，J＝7.6，7.6Hz，1H)，3.67(dd，J＝5.6，5.6Hz，1H)，5.24-5.32(m，1H)，7.28-7.32(m，2H)，7.45(t，J＝7.2Hz，2H)，7.51-7.58(m，2H)，7.81(dd，J＝1.6，2.4Hz，1H)，7.90(d，J＝6.8Hz，2H)，8.07(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝20.7，44.8，47.9，110.2，120.6，122.2，122.9，127.9，128.8，133.7，136.2，141.2，144.0，196.3.
Embodiment 53:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and 1,2,4-triazole (0.6mmol, 41.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 69.9mg, productive rate is 65% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.66(d，J＝6.8Hz，2H)，3.33(dd，J＝5.2，5.2Hz，1H)，3.81(dd，J＝7.6，7.6Hz，1H)，5.16-5.24(m，1H)，7.46(t，J＝7.6Hz，2H)，7.58(t，J＝7.6Hz，1H)，7.90-7.92(m，3H)，8.21(s，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.0，44.5，51.6，128.0，128.7，133.7，136.2，142.9，151.9，196.5.
Embodiment 54:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and benzotriazole (0.6mmol, 71.4mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.Column chromatography for separation after reaction finishes (adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 72.3mg, productive rate is 61%.
1H?NMR(400MHz，CDCl
3)δ＝1.79(d，J＝6.8Hz，3H)，3.66(dd，J＝6.0，6.0Hz，1H)，4.11(dd，J＝6.8，7.2Hz，1H)，5.58-5.66(m，1H)，7.34-7.36(m，1H)，7.38-7.42(m，2H)，7.44-7.58(m，2H)，7.71(d，J＝8.4Hz，1H)，7.93(d，J＝8.8Hz，1H)，8.04(d，J＝8.4Hz，1H).
13C?NMR(100.8MHz，CDCl
3)δ＝21.4，44.7，50.5，109.7，119.8，123.9，127.2，128.0，128.7，132.6，133.6，136.2，145.8，196.6.
Embodiment 55:
Under the room temperature, with 1-phenyl-2-butylene-1-ketone (0.5mmol, 73.0mg) and 5-phenyl tetrazole (0.6mmol, 87.6mg) and [Hmim] OTs (30mol%, 38.1mg), place dry reaction flask, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain sterling 89.1mg, productive rate is 61% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.77(d，J＝6.8Hz，3H)，3.59(dd，J＝6.8，7.2Hz，1H)，3.98(dd，J＝6.4，6.4Hz，1H)，5.66-5.74(m，1H)，7.44-7.48(m，5H)，7.56-7.59(m，1H)，7.96(d，J＝7.6Hz，2H)，8.13(d，J＝8.0Hz，2H).
13C?NMR(100.8MHz，CDCl
3)δ＝20.0，43.0，55.3，125.8，126.5，127.1，127.7，127.8，129.2，132.7，135.1，163.8，194.6.
Embodiment 56
Under the room temperature, with 3-amylene-2-ketone (0.5mmol, 42mg) with 5-phenyl tetrazole (0.6mmol, 87.6mg) ionic liquid of extraction phase after through 80 ℃ of vacuum-drying 24h joins in the reaction flask successively among the embodiment 30, stirring at room 1h, TLC monitors reaction, with ethyl acetate extraction reaction solution three times, merge organic phase, column chromatography for separation obtains sterling 107.0mg, and yield is 93%; Ionic liquid recycles 5 times, does not find that yield obviously descends.Specifically see Table 1, NMR data and see embodiment 30.
Table 1 catalyst recirculation service condition
Claims (7)
1. beta-amino carbonyl compound, β-sulfydryl ketone, the synthetic method of β-ketonic ether, it is characterized in that: use amino formate, nitrogen-containing heterocycle compound, phenyl amines, thiophenol or benzenethiol, Fatty Alcohol(C12-C14 and C12-C18) nucleophilic reagent and α, beta-unsaturated carbonyl compound is as reactant, with functionalized ion liquid as catalyzer, wherein the cationic moiety of functionalized ion liquid is selected from glyoxaline cation or pyridylium, anionicsite is selected from the trifluoromethanesulfonic acid root, bisulfate ion, the tosic acid root, tetrafluoroborate, hexafluoro-phosphate radical or dihydrogen phosphate, under 20-30 ℃, reaction times 1～48h, the hetero-Michael addition reaction generates corresponding beta-amino carbonyl compound, β-sulfydryl ketone, β-ketonic ether compound.
2. the method for claim 1 is characterized in that catalyzer is a kind of in the following description:
R wherein
1, R
2, R
3Group represents respectively C
1～C
20With interior fat group, comprise methyl, ethyl or butyl, X
-Represent tosic acid root (OTs
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6 -), bisulfate ion (HSO
4 -) or dihydrogen phosphate (H
2PO
4 -), n represents 1～6 integer.
3. the method for claim 1, it is characterized in that nitrogen-containing heterocycle compound is selected from urethanum, benzyl carbamate, t-butyl carbamate, butyl carbamate, oxazolinone, imidazoles, benzoglyoxaline, pyrazoles, 1,2,4-triazole, benzotriazole or benzo tetrazole.
4. the method for claim 1 is characterized in that thiophenol or mercaptan are selected from thiophenol, 4-methylbenzene phenyl-sulfhydrate, 4-chlorothio-phenol, 2-thionaphthol, 4-methoxybenzenethiol, 2-methylbenzene phenyl-sulfhydrate, beneze methane thiol or hexylmercaptan.
5. the method for claim 1 is characterized in that Fatty Alcohol(C12-C14 and C12-C18) is selected from methyl alcohol, ethanol, chloroethanol, Virahol or phenylcarbinol.
6. the method for claim 1, it is characterized in that α, beta-unsaturated carbonyl compound is selected from 2-tetrahydrobenzene-1-ketone, 3-methyl-2-tetrahydrobenzene-1-ketone, 2-cyclopentene-1-one, 3-methyl-2-cyclopentene-1-one, 3-amylene-2-ketone, methylene acetone, 4-methyl-3-amylene-2-ketone, 4-hexene-3-one, 1-phenyl-2-butylene-1-ketone, N-phenyl butylene imide, methyl acrylate or vinyl cyanide.
7. the method for claim 1 is characterized in that nucleophilic reagent and α, and the mol ratio of beta-unsaturated carbonyl compound is 1: 1～4: 1.
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