CN103073372A - Method for synthesizing amine compound catalyzed by functionalized ionic liquid - Google Patents
Method for synthesizing amine compound catalyzed by functionalized ionic liquid Download PDFInfo
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- CN103073372A CN103073372A CN2011103271020A CN201110327102A CN103073372A CN 103073372 A CN103073372 A CN 103073372A CN 2011103271020 A CN2011103271020 A CN 2011103271020A CN 201110327102 A CN201110327102 A CN 201110327102A CN 103073372 A CN103073372 A CN 103073372A
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- KXDAEFPNCMNJSK-UHFFFAOYSA-N NC(c1ccccc1)=O Chemical compound NC(c1ccccc1)=O KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N OC(c1ccccc1)c1ccccc1 Chemical compound OC(c1ccccc1)c1ccccc1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- FALTVGCCGMDSNZ-UHFFFAOYSA-N CC(c1ccccc1)NC(c1ccccc1)=O Chemical compound CC(c1ccccc1)NC(c1ccccc1)=O FALTVGCCGMDSNZ-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N CC(c1ccccc1)O Chemical compound CC(c1ccccc1)O WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- QWKKYJLAUWFPDB-UHFFFAOYSA-N NS(c(cc1)ccc1[N+]([O-])=O)(=O)=O Chemical compound NS(c(cc1)ccc1[N+]([O-])=O)(=O)=O QWKKYJLAUWFPDB-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N Nc(cc1)ccc1[N+]([O-])=O Chemical compound Nc(cc1)ccc1[N+]([O-])=O TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- IUZPOCRNJUWIIN-WUKNDPDISA-N O=C(c1ccccc1)NC(/C=C/c1ccccc1)c1ccccc1 Chemical compound O=C(c1ccccc1)NC(/C=C/c1ccccc1)c1ccccc1 IUZPOCRNJUWIIN-WUKNDPDISA-N 0.000 description 1
- RCFJRHRJIZVTEP-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1NC(c1ccccc1)c1ccccc1)=O Chemical compound [O-][N+](c(cc1)ccc1NC(c1ccccc1)c1ccccc1)=O RCFJRHRJIZVTEP-UHFFFAOYSA-N 0.000 description 1
- DUJLUFZGRFVVEV-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1S(NC(c1ccccc1)c1ccccc1)(=O)=O)=O Chemical compound [O-][N+](c(cc1)ccc1S(NC(c1ccccc1)c1ccccc1)(=O)=O)=O DUJLUFZGRFVVEV-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a method for synthesizing an amine compound catalyzed by functionalized ionic liquid. According to the method, functionalized ionic liquid is used as a catalyst to catalyze N-alkylation of amine and alcohol to synthesize corresponding compound derivatives. Acid functionalized ionic liquid is used as the catalyst to synthesize a series of compounds of amine. The method has the following advantages: a catalytic system is a metal-free system; the usage amount of the catalyst is small, and the catalyst has high catalytic activity, good stability and low corrosivity; operation is simple, and reaction is mild; post-treatment is easy, and the catalyst can be cyclically used.
Description
Technical field
The invention belongs to the synthetic field of aminated compounds, be specifically related to a kind of functionalized ion liquid that utilizes and be catalyzer, the N-alkylated reaction of catalytic amine (comprising amides, sulfonamides, phenyl amines and amino formate) and alcohol, the method for having synthesized the respective compound derivative.
Background technology
The N-alkylated reaction is a kind of important method of synthetic organic amine and derivative thereof.Organic amine and derivative thereof are important organic intermediate fragments, in organic synthesis, pharmacy, macromolecular material and meticulous product chemistry important purposes are arranged.Wherein sulfone amide derivative is important pharmaceutical intermediate, in sterilization, anti-inflammatory, antiviral, diuresis, anti-epileptic, hypotensive, hypoglycemic, reducing blood-fat and suppress to play a part can not be ignored aspect the hiv protease.The traditional synthetic method of organic amine is made by acyl chlorides or SULPHURYL CHLORIDE and amine reaction, generates salt and a large amount of sulfur-bearing or the waste of chlorine of equivalent, and contaminate environment not only, and inadequate Atom economy have caused unnecessary waste; And the industrial synthetic method of taking is, under High Temperature High Pressure, utilizes hydrogenation catalyst catalytic alcohol and amine reaction synthesizing aminated compounds, and energy consumption is very large.At present, the catalyst system of having reported has: NaAuCl
4(Adv.Synth.Catal., 2006,348,2063), InCl
3(Angew.Chem.Int.Ed., 2007,46,409), Bi (OTf)
3(J.Org.Chem., 2007,72,6006), Sc (OTf)
3(Org.Chem., 2007,9,2027), proton-exchanged montmorillonite (Org.Lett., 2006,8,4617), Ru/Fe
3O
4(J.Am.Chem.Soc., 2009,131,1775), Ca (NTf
2)
2/ Bu
4NPF
6(Adv.Synth.Catal., 2011,353,469).Above-mentioned catalyst system has related to transition metal, precious metal or strong protonic acid mostly, and price comparison is expensive, and environment is unfriendly.
Because ionic liquid at room temperature has the advantages such as extremely low volatility, uninflammability, high stability and chemical stability, high ionic conductivity, broad electrochemical window, polarity adjustability, therefore obtained paying close attention to and becoming rapidly widely the study hotspot in the fields such as organic chemistry, electrochemistry, materials chemistry, catalytic chemistry and polymer chemistry.Ionic liquid is applied to catalyzed reaction and starts from 1972, enters subsequently summit in beginning of this century last century Mo, and a large amount of ionic liquids is synthesized and is applied to nearly all catalyzed reaction to substitute volatility, poisonous organic solvent.Ionic liquid also has designability, makes it can not only serve as solvent in reaction by the functionalized design to positively charged ion or negatively charged ion, can also play the effect of catalyzer.Once reported the amination reaction of ionic liquid-catalyzed alcohol among the Green Chemstry in 2011, but the catalyzer that uses is ionic liquid ([the CHCl] [ZnCl that contains metallic zinc
2]
2), namely this report is still introduced transition metal ion in the reaction.
Summary of the invention
The object of the invention is to overcome in the prior art to exist and use the defectives such as transition metal and strong protonic acid or corrodibility strong catalyzer, severe reaction conditions, long reaction time, side reaction be many, under relatively mild condition, thereby provide a kind of ionic liquid-catalyzed amine and the N-alkylation of alcohol to generate more effective, the more economical and eco-friendly method of amino derivative.
Chemical equation of the present invention is as follows:
R
1Represent alkylsulfonyl, acyl group, aryl, ester group contains the N heterocycle
R
2Represent alkyl, allyl group, hexichol aryl
The present invention utilizes functionalized ion liquid to be catalyzer, the N-alkylated reaction of catalytic amine (comprising amides, sulfonamides, phenyl amines and amino formate) and alcohol, the method for having synthesized the respective compound derivative.
A kind of synthetic method of amino derivative, it is characterized in that: use sulfonamides, amides, phenyl amines, amino formate or nitrogen heterocyclic ring compounds, with alcohol compound as initial reactant, as catalyzer, wherein the cationic moiety of functionalized ion liquid is selected from glyoxaline cation, pyridylium, morpholine positively charged ion, tetramethyleneimine positively charged ion, guanidine cationoid, quaternary alkylphosphonium salt cationoid, two morpholine positively charged ion, two tetramethyleneimine positively charged ion or two glyoxaline cation with functionalized ion liquid; Anionicsite is selected from the tosic acid root; 25～150 ℃ of temperature of reaction, reaction times 0.1～48h, the derivative that the N-alkylated reaction generates corresponding amides class, sulfonamides, phenyl amines, amino formate compounds occurs with alcohol in amine.
Catalyzer is a kind of in the following description:
Wherein R represents butyl or phenyl, and X-represents tosic acid root (TsO
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6-), bisulfate ion (HSO
4 -), methanesulfonic root (CH
3SO
3 -) or camphorsulfonic acid root (CMs
-), n represents 1～18 integer.
In aforesaid method, sulfamide compound is selected from 4-methyl benzenesulfonamide, 4-nitrobenzene sulfonamide, benzsulfamide or amsacrine.
In aforesaid method, amides is selected from 4-methyl benzamide, 4-chlorobenzamide, benzamide, oxazolidine-2-ketone, methane amide, ethanamide, propionic acid amide, acrylamide, pyrrolidin-2-one, hexanolactam or picolinamide.
In aforesaid method, amino benzenes compounds is selected from 4-N-methyl-p-nitroaniline, 2-N-methyl-p-nitroaniline or 4-5-trifluoromethylaniline.
In aforesaid method, nitrogen-containing heterocycle compound is selected from 1H-pyrazoles, 4H-1,2,4-triazole, benzotriazole or 5-phenyl-1H-tetrazole.
In aforesaid method, alcohol compound is selected from methyl alcohol, ethanol, chloroethanol, Virahol, hexalin, 1-phenylethyl alcohol, (E)-1,3-phenylbenzene-2-propylene-1-alcohol, 1,3-phenylbenzene-2-propine-1-alcohol, 2-methyl isophthalic acid-phenyl-2-propylene-1-alcohol, vinyl carbinol, styryl carbinol, benzhydrol, 4-methyldiphenyl methyl alcohol, 4-chlorodiphenyl methyl alcohol or 2-chlorodiphenyl methyl alcohol.
In aforesaid method, amine is 1: 1～5: 1 with the mol ratio of alcohol.
In aforesaid method, reaction solvent is selected from Isosorbide-5-Nitrae-dioxane, Nitromethane 99Min., ether, toluene, acetonitrile, methylene dichloride, tetrahydrofuran (THF), DMF, [Bmim] [BF
4], [Bmim] [PF
6], methyl-sulphoxide, PEG-4000,1,2-ethylene dichloride, hexanaphthene, normal hexane, trichloromethane, tetracol phenixin, sym.-tetrachloroethane, methyl iso-butyl ketone (MIBK) or dimethylbenzene.
The present invention has the following advantages: catalyst system is without metal system; 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; Aftertreatment is simple, and catalyzer can recycle.
In a word, catalytic erosion of the present invention is low, catalytic activity is high and can be recycled, good product selectivity, and the easy easy operation of reaction process, controllability is strong, has avoided the use of transition metal and strong acid.
Embodiment
Being expressed as follows of catalyzer:
Wherein R represents butyl or phenyl, and X-represents tosic acid root (TsO
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6-), bisulfate ion (HSO
4 -), methanesulfonic root (CH
3SO
3 -) or camphorsulfonic acid root (CMs
-), n represents 1～18 integer.
Wherein used several ionic liquids referred to as:
The N-alkylated reaction of amine and alcohol prepares the process of aminated compounds:
In the dry reaction bottle of magnetic agitation is housed, add successively amine (amides, sulfonamides, phenyl amines and amino formate), alcohols and ionic liquid.Wherein amine is 1: 1～5: 1 with the mol ratio of alcohol, the consumption of catalyzer is 1～100mol%, 80～150 ℃ of lower reaction 0.1～48h, and thin-layer chromatography is followed the tracks of reaction process, add redistilled water separated product and ionic liquid, column chromatography or recrystallization separation obtain sterling; The water layer vacuum is spin-dried for, and carries out the next batch reaction behind 80 ℃ of lower vacuum-drying 24h of ionic liquid, after ionic liquid is reused 5 times, has no reaction yield and obviously descends.
Embodiment 1:
Under 80 ℃, will be to methyl benzenesulfonamide (0.75mmol, 128.3mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (20mol%, 55.0mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid N-diphenyl-methyl-4-methyl benzenesulfonamide 154.9mg, productive rate is 91.9% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.37(s，3H)，5.15(d，J＝6.8Hz，1H)，5.56(d，J＝6.8Hz，1H)，7.09-7.21(m，12H)，7.56(d，J＝8.0Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.5，61.4，127.2，127.4，127.6，128.5，129.4，137.3，140.5，143.2.HRMS-ESI：Calcd.For?C
20H
19NNaO
2S[M+Na]
+：360.1029.Found：360.1020.
Embodiment 2:
With example 1, catalyst system therefor is [TG] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 79.3%.
Embodiment 3:
With example 1, catalyst system therefor is [LPS] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 61.7%.
Embodiment 4:
With example 1, catalyst system therefor is [PyS] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 65.6%.
Embodiment 5:
With example 1, catalyst system therefor is [LBPS] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 77.2%.
Embodiment 6:
With example 1, catalyst system therefor is [Bis-BsPD] [OTf]
2, the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 62.4%.
Embodiment 7:
With example 1, catalyst system therefor is [Bis-BsIMD] [OTf]
2, the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 66.5%.
Embodiment 8:
With example 1, catalyst system therefor is [Bis-BsMD] [OTf]
2, the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 60.0%.
Embodiment 9:
With example 1, catalyst system therefor is [BsMP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 61.8%.
Embodiment 10:
With example 1, catalyst system therefor is [BsHP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 78.9%.
Embodiment 11:
With example 1, catalyst system therefor is [BsDP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 81.8%.
Embodiment 12:
With example 1, catalyst system therefor is [BsTdP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 83.5%.
Embodiment 13:
With example 1, catalyst system therefor is [BsCtP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 84.1%.
Embodiment 14:
With example 1, catalyst system therefor is [BsOdP] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 84.7%.
Embodiment 15:
With example 1, catalyst system therefor is [BsMIm] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 55.9%.
Embodiment 16:
With example 1, catalyst system therefor is [BsHIm] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 66.7%.
Embodiment 17:
With example 1, catalyst system therefor is [BsDIm] [OTf]], the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 85.8%.
Embodiment 18:
With example 1, catalyst system therefor is [BsCtIM] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 77.2%.
Embodiment 19:
With example 1, catalyst system therefor is [BsOdIM] [OTf], and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 81.7%.
Embodiment 20:
With example 1, catalyst system therefor is [BsMM] OTf, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 54.0%.
Embodiment 21:
With example 1, catalyst system therefor is [BsHM] OTf, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 57.0%.
Embodiment 22:
With example 1, solvent for use is Nitromethane 99Min., and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 82.5%.
Embodiment 23:
With example 1, solvent for use is ether, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 79.6%.
Embodiment 24:
With example 1, solvent for use is toluene, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 80.7%.
Embodiment 25:
With example 1, solvent for use is acetonitrile, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 73.6%.
Embodiment 26:
With example 1, solvent for use is methylene dichloride, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 85.7%.
Embodiment 27:
With example 1, solvent for use is tetrahydrofuran (THF), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 73.0%.
Embodiment 28:
With example 1, solvent for use is DMF, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 21.3%.
Embodiment 29:
With example 1, solvent for use is [Bmim] [BF
4], the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 71.9%.
Embodiment 30:
With example 1, solvent for use is [Bmim] [PF
6], the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 86.1%.
Embodiment 31:
With example 1, solvent for use is methyl-sulphoxide, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 32.4%.
Embodiment 32:
With example 1, solvent for use is 1,2-ethylene dichloride, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 86.6%.
Embodiment 33:
With example 1, solvent for use is hexanaphthene, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 80.3%.
Embodiment 34:
With example 1, solvent for use is normal hexane, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 77.9%.
Embodiment 35:
With example 1, solvent for use is trichloromethane, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 87.8%.
Embodiment 36:
With example 1, solvent for use is tetracol phenixin, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 88.6%.
Embodiment 37:
With example 1, solvent for use is sym.-tetrachloroethane, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 73.5%.
Embodiment 38:
With example 1, solvent for use is methyl iso-butyl ketone (MIBK), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 67.7%.
Embodiment 39:
With example 1, solvent for use is dimethylbenzene, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 85.1%.
Embodiment 40
With example 1, system temperature is 40 ℃, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 31%.
Embodiment 41
With example 1, system temperature is 60 ℃, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 73%.
Embodiment 42
With example 1, system temperature is 100 ℃, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 93%.
Embodiment 43
With example 1, system temperature is 120 ℃, and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 95%.
Embodiment 44
With example 1, catalyst system therefor is [BsTdmim] OTf (2.5mol%, 7mg), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 32.6%.
Embodiment 45:
With example 1, catalyst system therefor is [BsTdmim] OTf (5mol%, 13.8mg), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 32.6%.
Embodiment 46:
With example 1, catalyst system therefor is [BsTdmim] OTf (10mol%, 27.5mg), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 90.2%.
Embodiment 47:
With example 1, catalyst system therefor is [BsTdmim] OTf (20mol%, 55mg), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 91.9%.
Embodiment 48:
With example 1, catalyst system therefor is [BsTdmim] OTf (30mol%, 82.5mg), and the productive rate of N-diphenyl-methyl-4-methyl benzenesulfonamide is 93.1%.
Embodiment 49:
Under 80 ℃, with p-nitrophenyl sulphonamide (0.75mmol, 151.5mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid N-diphenyl-methyl-4-nitro-benzsulfamide 156.4mg, productive rate is 85% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.02(s，1H)，5.64(s，1H)，6.49-6.53(m，2H)，7.29-7.39(m，10H)，8.02(d，J＝9.2Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝62.4，122.1，126.2，127.4，128.0，129.1，138.6，141.0，152.1.HRMS-ESI：Calcd.For?C
19H
16N
2Na?O
4S[M+Na]
+：391.0723.Found：391.0729.
Embodiment 50:
Under 80 ℃, with oxazolidine-2-ketone (0.75mmol, 62.3mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid 3-diphenyl-methyl-oxazolidine-2-ketone 94.9mg, productive rate is 75% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝3.38(t，J＝8.0Hz，2H)，4.36(t，J＝8.0Hz，2H)，6.37(s，1H)，7.22(d，J＝6.8Hz，4H)，7.31-7.39(m，6H).
13C?NMR(100MHz，CDCl
3)δ＝41.7，60.7，62.1，127.9，128.4，128.7，138.1，158.3.HRMS-ESI：Calcd.For?C
16H
15NNaO
2[M+Na]
+：276.0995.Found：276.0989.
Embodiment 51:
Under 80 ℃, will be to methyl benzenesulfonamide (0.75mmol, 128.3mg) and 4-chloro-benzhydrol (0.5mmol, 109.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid N-((4-chloro-phenyl-) (phenmethyl))-4-methyl benzenesulfonamide 155.8mg, productive rate is 84% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.38(s，3H)，5.43(d，J＝7.6Hz，1H)，5.53(d，J＝7.2Hz，1H)，7.04-7.25(m，11H)，7.54(d，J＝8.0Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.5，60.8，127.2，127.3，127.8，128.6，128.7，128.8，129.4，133.4，137.2，139.0，140.1，143.4.HRMS-ESI：Calcd.ForC
20H
18ClNNaO
2S[M+Na]
+：394.0639.Found：394.0646.
Embodiment 52:
Under 80 ℃, will be to methyl benzenesulfonamide (0.75mmol, 128.3mg) and 4-methyl-benzhydrol (0.5mmol, 99.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain solid 4-methyl-N-(phenyl (p-methylphenyl) methyl) benzsulfamide 156.2mg of white, productive rate is 89% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝2.27(s，3H)，2.37(s，3H)，5.22(d，J＝6.8Hz，1H)，5.51(d，J＝7.2Hz，1H)，6.98(q，J＝8.0Hz，4H)，7.09-7.25(m，7H)，7.55(d，J＝8.4Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.0，21.5，61.1，127.2，127.3，127.3，127.4，128.5，129.2，129.3，137.3，137.4，137.6，140.7，143.1.HRMS-ESI：Calcd.For?C
21H
21NNaO
2S[M+Na]
+：374.1185.Found：374.1174.
Embodiment 53:
Under 80 ℃, will be to methyl benzenesulfonamide (0.75mmol, 128.3mg) and 2-chloro-benzhydrol (0.5mmol, 109.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid N-((2-chloro-phenyl-) (phenmethyl))-4-methyl benzenesulfonamide 120.6mg, productive rate is 65% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.37(s，3H)，5.54(d，J＝7.2Hz，1H)，5.94(d，J＝7.2Hz，1H)，7.07-7.24(m，10H)，7.33-7.37(m，1H)，7.61(d，J＝8.4Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.5，58.5，127.0，127.2，127.3，127.8，128.6，128.8，129.3，129.4，129.8，132.8，137.0，137.6，139.3，143.3.HRMS-ESI：Calcd.For?C
20H
18ClNNaO
2S[M+Na]
+：394.0639.Found：394.0637.
Embodiment 54:
Under 80 ℃, will be to methyl benzenesulfonamide (0.75mmol, 128.3mg) and 1,3-phenylbenzene-2-propine-1-alcohol (0.5mmol, 104.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid N-(1,3-phenylbenzene-2-propine)-4-methyl benzenesulfonamide 157.0mg, productive rate is 87% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.32(s，3H)，4.91(d，J＝9.2Hz，1H)，5.56(d，J＝9.2Hz，1H)，7.11-7.13(m，2H)，7.23-7.26(m，3H)，7.27-7.38(m，5H)，7.55-7.57(m，2H)，7.82(d，J＝8.4Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.4，49.8，85.4，86.7，122.0，127.4，127.6，128.1，128.5，128.6，128.7，130.0，131.6，137.4，137.4，143.6.HRMS-ESI：Calcd.For?C
22H
19NNaO
2S[M+Na]
+：384.1029.Found：384.1017.
Embodiment 55:
Under 80 ℃, with benzsulfamide (0.75mmol, 117.8mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain the solid N-diphenyl-methyl benzsulfamide 134.0mg of white, productive rate is 83% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.24(d，J＝7.2Hz，1H)，5.60(d，J＝7.2Hz，1H)，7.08-7.10(m，4H)，7.19-7.23(m，6H)，7.33(t，J＝8.0Hz，2H)，7.44-7.48(m，1H)，7.66-7.68(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝61.4，127.1，127.4，127.5，127.7，128.6，128.8，129.3，132.4，140.3.HRMS-ESI：Calcd.For?C
19H
17NNaO
2S[M+Na]
+：346.0872.Found：346.0864.
Embodiment 56:
Under 120 ℃, with amsacrine (0.75mmol, 71.3mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain the solid N-diphenyl-methyl amsacrine 99.2mg of white, productive rate is 76% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.64(s，1H)，5.32(d，J＝7.2Hz，1H)，5.75(d，J＝7.2Hz，1H)，7.27-7.38(m，10H).
13C?NMR(100MHz，CDCl
3)δ＝41.9，61.2，127.4，128.0，128.9，140.6.HRMS-ESI：Calcd.For?C
14H
15NNaO
2S[M+Na]
+：284.0716.Found：284.0708.
Embodiment 57:
Under 80 ℃, with 5-phenyl-1H-tetrazole (0.75mmol, 109.5mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=10/1), obtain white solid 2-diphenyl-methyl-5-phenyl-2H-tetrazole 149.8mg, productive rate is 96% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝7.33-7.50(m，14H)，8.15-8.18(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝71.2，127.0，127.5，128.3，128.7，128.8，128.8，130.3，137.2，165.3.HRMS-ESI：Calcd.For?C
20H
16N
4Na[M+Na]
+：335.1267.Found：335.1259.
Embodiment 58:
Under 80 ℃, with 4-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain yellow solid N-diphenyl-methyl-4-N-methyl-p-nitroaniline 132.2mg, productive rate is 87% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.02(s，1H)，5.63(s，1H)，6.48-6.52(m，2H)，7.28-7.38(m，10H)，7.80-8.03(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝62.4，112.1，126.2，127.4，128.0129.1，138.5，141.0，152.0.HRMS-ESI：Calcd.ForC
19H
16N
2NaO
2[M+Na]
+：327.1104.Found：327.1097.
Embodiment 59:
Under 80 ℃, with 2-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain yellow solid N-diphenyl-methyl-2-N-methyl-p-nitroaniline 135.3mg, productive rate is 89% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.73(d，J＝5.6Hz，1H)，6.63-6.67(m，1H)，6.72(d，J＝8.4Hz，1H)7.24-7.35(m，11H)，8.19(dd，J＝1.6，8.4Hz，1H)，8.61(d，J＝4.8Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝62.0，115.2，116.0，126.8，127.2，127.9，129.1，132.6，136.1，141.3，144.2.HRMS-ESI：Calcd.For?C
19H
16N
2NaO
2[M+Na]
+：327.1104.Found：327.1100.
Embodiment 60:
Under 80 ℃, with 4-5-trifluoromethylaniline (0.75mmol, 120.8mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain colourless liquid N-diphenyl-methyl-4-5-trifluoromethylaniline 135.3mg, productive rate is 89% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝4.53(s，1H)，5.53(s，1H)，6.53(d，J＝8.4Hz，2H)，7.24-7.34(m，12H).
13C?NMR(100MHz，CDCl
3)δ＝62.6，112.7，126.3，126.5，126.5，127.4，127.7，128.9，142.0，149.6.HRMS-ESI：Calcd.ForC
20H
16F
3NNa[M+Na]
+：350.1156.Found：350.1152.
Embodiment 61:
Under 120 ℃, with benzamide (0.75mmol, 90.8mg) and 1-phenylethyl alcohol (0.5mmol, 61.0mg) and [BsTdmim] OTf (10mo1%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain solid N-(1-phenylethyl) the benzamide 70.9mg of white, productive rate is 63% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.61(d，J＝6.8Hz，3H)，5.31-5.38(m，1H)，6.35(d，J＝6.0Hz，1H)，7.26-7.30(m，1H)，7.34-7.44(m，6H)，7.48-7.51(m，1H)，7.76-7.78(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.7，49.2，126.3，127.0，127.5，128.6，128.8，131.5，134.6，143.1，166.6.HRMS-ESI：Calcd.For?C
15H
15NNaO[M+Na]
+：248.1046.Found：248.1037.
Embodiment 62:
Under 140 ℃, with 4-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and 1-phenylethyl alcohol (0.5mmol, 61.0mg) and [TG] [OTf] (10mol%, 20mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation, reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain lurid solid 4-nitro-N-(1-phenylethyl) aniline 78.5mg, productive rate is 65% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.68(d，J＝7.2Hz，3H)，4.00(q，J＝7.2Hz，1H)，4.16(s，1H)，6.59(d，J＝8.8Hz，1H)，7.17-7.19(m，2H)，7.22-7.26(m，2H)，7.30-7.33(m，2H)，8.03(dd，J＝2.8，8.8Hz，1H)，8.26(d，J＝2.4Hz，1H).
13CNMR(100MHz，CDCl
3)δ＝21.9，40.4，114.6，123.9，124.4，127.1，127.2，129.2，143.8，150.7.HRMS-ESI：Calcd.For?C
14H
14N
2NaO
2[M+Na]
+：265.0947.Found：265.0947.
Embodiment 63:
Under 140 ℃, with 4-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and methyl alcohol (0.5mmol, 16mg) and [TG] [OTf] (10mol%, 20mg), Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain yellow solid N-methyl-4-nitrophenylamine 14.5mg, productive rate is 19% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝2.95(s，3H)，4.62(s，1H)，6.51-6.55(m，2H)，8.08-8.12(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝3.02，110.7，126.4，154.2.HRMS-ESI：Calcd.For?C
7H
8N
2NaO
2[M+Na]
+：175.0478.Found：175.0476.
Embodiment 64:
Under 140 ℃, with 4-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and ethanol (0.5mmol, 23mg) and [TG] [OTf] (10mol%, 20mg), Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain yellow solid N-ethyl-4-N-methyl-p-nitroaniline 19.9mg, productive rate is 24% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝1.31(t，J＝7.2Hz，3H)，3.26(q，J＝7.2Hz，2H)，4.50(s，1H)，6.50-6.54(m，2H)，8.07-8.10(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝14.4，38.0，110.9，126.5，137.9，153.3.HRMS-ESI：Calcd.For?C
8H
10N
2NaO
2[M+Na]
+：189.0634.Found：189.0643.
Embodiment 65:
Under 140 ℃, with 4-N-methyl-p-nitroaniline (0.75mmol, 103.5mg) and hexalin (0.5mmol, 50mg) and [TG] [OTf] (10mol%, 20mg), Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 24h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain yellow solid N-hexyl-4-N-methyl-p-nitroaniline 53.9mg, productive rate is 49% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝1.18-1.30(m，4H)，1.35-1.46(m，2H)，1.66-1.71(m，1H)，1.77-1.82(m，2H)，2.04-2.08(m，2H)，3.33-3.40(m，1H)，4.45(s，1H)，6.50(d，J＝9.2Hz，2H)，8.05-8.09(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝24.8，25.6，32.9，51.6，111.1，111.2，126.6，137.5.HRMS-ESI：Calcd.For?C
12H
16N
2NaO
2[M+Na]
+：243.1104.Found：243.1103.
Embodiment 66:
Under 80 ℃, with benzamide (0.75mmol, 90.8mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain the solid N-diphenyl-methyl benzamide 116.2mg of white, productive rate is 81% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝6.46(d，J＝7.6Hz，1H)，6.66(d，J＝7.2Hz，1H)，7.29-7.37(m，11H)，7.43-7.46(m，2H)，7.50-7.54(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝57.5，127.0，127.5，127.6，128.7，131.7，134.3，141.5，166.5.HRMS-ESI：Calcd.For?C
20H
17NNaO[M+Na]
+：310.1202.Found：310.1207.
Embodiment 67:
Under 80 ℃, with 4-methyl benzamide (0.75mmol, 101.3mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain the solid N-diphenyl-methyl benzamide 133.9mg of white, productive rate is 89% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.40(s，3H)，6.45(d，J＝8.0Hz，1H)，6.63(d，J＝7.6Hz，1H)，7.24(d，J＝8.0Hz，2H)，7.27-7.37(m，10H)，7.72(d，J＝8.0Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.5，57.4，126.5，127.0，127.5，128.5，128.7，129.3，131.4，141.6，166.4.HRMS-ESI：Calcd.For?C
21H
19NNaO[M+Na]
+：324.1359.Found：324.1344.
Embodiment 68::
Under 80 ℃, with urethanum (0.75mmol, 66.8mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=10/1), obtain the solid N-diphenyl-methyl benzamide 109.7mg of white, productive rate is 86% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.23(t，J＝Hz，3H)，4.12(q，J＝7.2Hz，2H)，5.34(s，1H)，5.97(d，J＝6.8Hz，1H)，7.03-7.27(m，6H)，7.30-7.35(m，4H).
13CNMR(100MHz，CDCl
3)δ＝14.6，58.7，61.1，127.3，127.4，128.6，141.8，155.8.HRMS-ESI：Calcd.For?C
16H
17NNaO
2[M+Na]
+：278.1151.Found：278.1155.
Embodiment 69:
Under 80 ℃, with urethanum (0.75mmol, 66.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.Column chromatography for separation after reaction finishes (adopt silicagel column, eluent: petrol ether/ethyl acetate=20/1), obtain the solid (E)-1 of white, 3-diphenylprop enamino ethyl formate 119.4mg, productive rate is 85%.
1H?NMR(400MHz，CDCl
3)δ＝1.72(t，J＝7.2Hz，3H)，4.15(q，J＝7.2Hz，2H)，5.12(s，1H)，5.52(s，1H)，6.33(dd，J＝6.0，16.0Hz，1H)，6.56(d，J＝16.0Hz，1H)，7.21-7.38(m，10H).
13C?NMR(100MHz，CDCl
3)δ＝14.6，56.6，61.1，126.6，127.0，127.7，127.8，128.6，128.8，129.3，131.1，136.5，141.1，155.8.HRMS-ESI：Calcd.For?C
18H
19NNaO
2[M+Na]
+：304.1308.Found：304.1301.
Embodiment 70:
Under 80 ℃, with 4-methyl benzenesulfonamide (0.75mmol, 128.3mg) and 2-methyl isophthalic acid-phenyl-3-propylene-1-alcohol (0.5mmol, 74.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain lurid solid 4-methyl-N-(2-methyl isophthalic acid-phenyl-allyl group) benzsulfamide 106.9mg, productive rate is 71% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.79(s，3H)，2，42(s，3H)，3.65(d，J＝6.4Hz，2H)，4.82(d，J＝5.6Hz，1H)，6.34(s，1H)，7.13(d，J＝7.6Hz，2H)，7.20(t，J＝7.2Hz，1H)，7.28-7.32(m，4H)，7.78(d，J＝4.8Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝16.0，21.5，51.6，126.7，127.2，127.9，128.1，128.8，129.7，133.2，137.0，137.2，143.4.HRMS-ESI：Calcd.ForC
17H
19NNaO
2S[M+Na]
+：324.1029.Found：324.1025.
Embodiment 71:
Under 80 ℃, with 1H-pyrazoles (0.75mmol, 51.0mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid (E)-1-(1,3-phenylbenzene allyl group)-1H-pyrazoles 117.0mg, productive rate is 90% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝6.18(d，J＝7.2Hz，1H)，6.30(t，J＝2.0Hz，1H)，6.44(d，J＝16.0Hz，1H)，6.71(dd，J＝15.6，6.8Hz，1H)，7.21-7.26(m，3H)，7.28-7.40(m，7H)，7.46(d，J＝2.4Hz，1H)，7.60(d，J＝1.6Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝67.6，105.6，126.7，127.3，127.4，128.1，128.1，128.5，128.6，128.8，133.7，136.0，139.4，139.6.HRMS-ESI：Calcd.ForC
17H
19NNaO
2S[M+Na]
+：324.1029.Found：324.1025.
Embodiment 72:
Under 80 ℃, with N, 4-dimethyl benzene sulfonamide (0.75mmol, 128.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=10/1), obtain colourless liquid (E)-N-(1,3-phenylbenzene allyl group)-N, 4-dimethyl benzene sulfonamide 167.8mg, productive rate are 89% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.31(s，3H)，2.70(s，3H)，5.83(d，J＝7.6Hz，1H)，6.13(dd，J＝16.0，7.6Hz，1H)，6.36(d，J＝16.0Hz，1H)，7.18-7.25(m，5H)，7.28-7.34(m，7H)，7.70(d，J＝8.4Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝21.4，26.9，30.1，62.3，123.8，126.5，127.5，127.8，127.8，128.0，128.5，129.6，134.7，136.2，136.6，138.5，143.2.HRMS-ESI：Calcd.For?C
23H
23NNaO
2S[M+Na]
+：400.1342.Found：400.1341.
Embodiment 73:
Under 120 ℃, with picolinamide (0.75mmol, 91.5mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg) Isosorbide-5-Nitrae-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/2), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) picolinamide 127.2mg, productive rate is 81% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝6.00(t，J＝6.8Hz，1H)，6.41(dd，J＝16.0，6.4Hz，1H)，6.59(d，J＝16.8Hz，1H)，7.04(d，J＝8.0Hz，1H)，7.21-7.41(m，11H)，8.10-8.13(m，1H)，8.64(m，1H)，8.98(d，J＝1.6Hz，1H).
13C?NMR(100MHz，CDCl
3)δ＝55.4，123.5，126.6，127.2，127.9，128.0，128.3，128.6，128.9，130.1，132.1，135.3，136.2，140.5，148.0，152.3，164.7.HRMS-ESI：Calcd.For?C
21H
19N
2O[M+H]
+：315.1492.Found：315.1482.
Embodiment 74:
Under 80 ℃, with hexanolactam (0.75mmol, 84.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) hexanolactam 108.3mg, productive rate is 71% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.25-1.31(m，1H)，1.43-1.47(m，1H)，1.63-1.70(m，4H)，2.65-2.67(m，2H)，3.26-3.37(m，2H)，6.45(dd，J＝6.8，16.4Hz，1H)，6.63(s，1H)，6.65(d，J＝6.8Hz，1H)，7.25-7.36(m，8H)，7.43(d，J＝7.2Hz，2H).
13C?NMR(100MHz，CDCl
3)δ＝23.4，29.0，29.9，37.5，45.4，58.3，126.1，126.5，127.5，127.8，128.0，128.5，128.6，133.6，136.7，139.8，175.9.HRMS-ESI：Calcd.For?C
21H
23NNaO[M+Na]
+：328.1672.Found：328.1671.
Embodiment 75:
Under 80 ℃, with acrylamide (0.75mmol, 53.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) acrylamide 124.9mg, productive rate is 95% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.67(dd，J＝1.2，10.0Hz，1H)，5.89(dd，J＝1.2，7.6Hz，1H)，6.10-6.20(m，2H)，6.31-6.39(m，2H)，6.55(d，J＝16.0Hz，1H)，7.21-7.25(m，1H)，7.27-7.36(m，9H).
13C?NMR(100MHz，CDCl
3)δ＝54.8，126.6，127.1，127.2，127.8，127.8，128.6，128.9，130.6，131.6，136.4，140.7，164，5.HRMS-ESI：Calcd.For?C
18H
17NNaO[M+Na]
+：286.1202.Found：286.1198.
Embodiment 76:
Under 80 ℃, with propionic acid amide (0.75mmol, 54.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) propionic acid amide 131.2mg, productive rate is 99% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝1.20(s，3H)，2.62-2.32(m，2H)，5.81-5.87(m，2H)，6.35(dd，J＝5.6，16.0Hz，1H)，6.53(d，J＝15.6Hz，1H)，7.22-7.24(m，1H)，7.29-7.38(m，9H).
13C?NMR(100MHz，CDCl
3)δ＝9.8，29.8，54.6，126.5，127.2，127.7，127.8，128.6，128.8，129.0，131.4，136.4，141.0，172.7.HRMS-ESI：Calcd.For?C
18H
19NNaO[M+Na]
+：288.1359.Found：288.1360.
Embodiment 77:
Under 80 ℃, with oxazolidine-2-ketone (0.75mmol, 65.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 0.3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), get colourless liquid (E)-3-(1,3-phenylbenzene allyl group) oxazolidine-2-ketone 136.7mg, productive rate is 98% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝3.26-3.30(m，1H)，3.55-3.62(m，1H)，4.26-4.36(m，2H)，5.81(d，J＝6.4Hz，1H)，6.45(dd，J＝6.8，19.6Hz，1H)，6.67(d，J＝15.2Hz，1H)，7.24-7.44(m，10H).
13C?NMR(100MHz，CDCl
3)δ＝26.9，41.0，58.4，62.1，124.8，126.6，127.8，128.1，128.7，128.9，133.8，136.1，138.0，158.2.HRMS-ESI：Calcd.For?C
18H
17NNaO
2[M+Na]
+：302.1151.Found：302.1149.
Embodiment 78:
Under 80 ℃, with 4H-1,2,4-triazole (0.75mmol, 51.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 1h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain colourless liquid (E)-4-(1,3-phenylbenzene allyl group)-4H-1,2,4-triazole 129.2mg, productive rate are 99% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝6.19(d，J＝7.2Hz，1H)，6.51(d，J＝16.0Hz，1H)，6.68(dd，J＝7.2，14.8Hz，1H)，7.27-7.40(m，10H)，8.03(s，1H)，8.15(s，1H).
13C?NMR(100MHz，CDCl
3)δ＝66.1，125.6，126.8，127.5，128.6，128.7，128.8，129.1，134.7，135.5，137.7，142.7，152.0.HRMS-ESI：Calcd.For?C
17H
16N
3[M+H]
+：262.1339.Found：262.1337.
Embodiment 79:
Under the room temperature, with 5-phenyl-1H-tetrazole (0.75mmol, 109.5mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 0.25h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=10/1), obtain white solid (E)-2-(1,3-phenylbenzene allyl group)-5-phenyl-2H-tetrazole 157.2mg, productive rate is 93% to column chromatography for separation after reaction finishes.
1H?NMR?(400MHz，CDCl
3)δ＝6.70(dd，J＝8.0，19.2Hz，2H)，6.91(dd，J＝7.6，16.0Hz，1H)，7.24-7.49(m，13H)，8.16-8.18(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝69.8，124.9，126.9，127.4，127.4，128.6，128.7，128.8，129.0，130.3，135.0，135.5，137.1，165.2.HRMS-ESI：Calcd.For?C
2H
18N
4Na[M+Na]
+：361.1424.Found：361.1420.
Embodiment 80:
Under 80 ℃, with amsacrine (0.75mmol, 71.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 2h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) amsacrine 142.1mg, productive rate is 99% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.75(s，3H)，5.18(d，J＝6.8Hz，1H)，5.27(t，J＝6.8Hz，1H)，6.32(dd，J＝6.8，15.6Hz，1H)，6.61(d，J＝16.0Hz，1H)，7.23-7.39(m，10H).
13C?NMR(100MHz，CDCl
3)δ＝42.2，59.8，126.7，127.2，128.2，128.3，128.5，128.7，129.0，132.5，135.9，139.9.HRMS-ESI：Calcd.For?C
16H
17NNaO
2S[M+Na]
+：310.0872.Found：310.0864.
Embodiment 81:
Under 80 ℃, with ethanamide (0.75mmol, 44.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=1/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) ethanamide 123.0mg, productive rate is 98% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.05(s，3H)，5.81(t，J＝6.8Hz，1H)，5.97(d，J＝7.6Hz，1H)，6.34(dd，J＝6.0，16.0Hz，1H)，6.53(d，J＝16.0Hz，1H)，7.21-7.37(m，10H).
13C?NMR(100MHz，CDCl
3)δ＝23.4，54.8，126.6，127.2，127.7，127.8，128.6，128.8，129.1，131.3，136.5，141.0，169.3.HRMS-ESI：Calcd.For?C
17H
17NNaO[M+Na]
+：274.1202.Found：274.1203.
Embodiment 82:
Under 80 ℃, with benzsulfamide (0.75mmol, 117.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) benzsulfamide 162.3mg, productive rate is 93% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.64(t，J＝7.2Hz，1H)，2.65(d，J＝6.8Hz，1H)，6.10(dd，J＝6.8，16.0Hz，1H)，6.37(d，J＝16.0Hz，1H)，7.16-7.25(m，10H)，7.33(t，J＝7.6Hz，2H)，7.42-7.45(m，1H)，7.75-7.77(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝59.8，126.5，127.1，127.2，127.9，128.1，128.5，128.7，128.8，132.2，132.4，136.0，139.5，140.7.HRMS-ESI：Calcd.ForC
21H
19NNaO
2S[M+Na]
+：372.1016.Found：372.1029.
Embodiment 83:
Under 80 ℃, with 4-methyl benzenesulfonamide (0.75mmol, 128.3mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group)-4-methyl benzenesulfonamide 157.9mg, productive rate is 87% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝2.32(s，3H)，5.06(d，J＝7.2Hz，1H)，5.11(t，J＝6.8Hz，1H)，6.07(J＝6.4，15.6Hz，1H)，6.34(d，J＝16.0Hz，1H)，7.13-7.25(m，12H)，7.65(d，J＝8.4Hz，2H).
13CNMR(100MHz，CDCl
3)δ＝21.4，59.8，126.5，127.1，127.3，127.9，128.0，128.2，128.5，128.7，129.4，132.1，136.0，137.7，139.6，143.3.HRMS-ESI：Calcd.ForC
22H
21NNaO
2S[M+Na]
+：386.1185.Found：386.1171.
Embodiment 84:
Under 80 ℃, with pyrrolidin-2-one (0.75mmol, 63.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 1.5h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=3/1), obtain white solid (E)-1-(1,3-phenylbenzene allyl group) pyrrolidin-2-one 157.9mg, productive rate is 98% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝1.93-2.10(m，2H)，2.40-2.54(m，2H)，3.09-3.15(m，1H)，3.40-3.45(m，1H)，6.09(d，J＝6.8Hz，1H)，6.45(dd，J＝6.8，16.0Hz，1H)，6.62(d，J＝16.0Hz，1H)，7.24-7.38(m，8H)，7.42(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝18.1，31.2，43.4，56.2，125.4，126.6，127.7，127.8，127.9，128.6，128.7，133.5，136.4，138.7，174.7.HRMS-ESI：Calcd.For?C
19H
19NNaO[M+Na]
+：300.1359.Found：300.1359.
Embodiment 85:
Under 80 ℃, with benzamide (0.75mmol, 90.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) benzamide 126.8mg, productive rate is 81% to column chromatography for separation after reaction finishes.
1HNMR(400MHz，CDCl
3)δ＝6.03(t，J＝6.8Hz，1H)，6.44(dd，J＝6.0，16.0Hz，1H)，6.52(d，J＝8.0Hz，1H)，7.18-7.24(m，1H)，7.29-7.53(m，12H)，7.81-7.84(m，2H).
13C?NMR(100MHz，CDCl
3)δ＝55.2，126.6，127.0，127.2，127.8，127.9，128.6，128.6，128.8，128.9，1311.7，131.8，134.4，136.4，140.8，166.5.HRMS-ESI：Calcd.For?C
22H
19NNaO[M+Na]
+：336.1359.Found：336.1354.
Embodiment 86:
Under 80 ℃, with methane amide (0.75mmol, 33.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation, magnetic agitation reaction 12h.(adopt silicagel column, eluent: petrol ether/ethyl acetate=5/1), obtain white solid (E)-N-(1,3-phenylbenzene allyl group) methane amide 93.6mg, productive rate is 79% to column chromatography for separation after reaction finishes.
1H?NMR(400MHz，CDCl
3)δ＝5.89(t，J＝7.2Hz，3H)，6.10(d，J＝7.6Hz，1H)，6.31-6.38(m，1H)，6.54-6.60(m，1H)，7.22-7.26(m，1H)，7.29-7.37(m，9H)，8.28(s，1H).
13C?NMR(100MHz，CDCl
3)δ＝53.5，126.6，126.6，127.1，127.9，128.2，128.6，128.9，131.7，136.2，140.3，160.1.HRMS-ESI：Calcd.For?Cl
6H
15NNaO[M+Na]
+：260.1046.Found：260.1036.
Embodiment 87:
Under 80 ℃, with t-butyl carbamate (0.75mmol, 87.8mg) and (E)-1,3-phenylbenzene-2-propylene-1-alcohol (0.5mmol, 105.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.Column chromatography for separation after reaction finishes (adopt silicagel column, eluent: petrol ether/ethyl acetate=20/1), obtain the solid (E)-1 of white, 3-diphenylprop enamino t-butyl formate 143.7mg, productive rate is 93%.
1H?NMR(400MHz，CDCl
3)：δ＝1.45(s，9H)，4.93(s，1H)，5.46(s，1H)，6.32(dd，J＝6.4，16.0HMz，1H)，6.54(dd，J＝1.2，16.0HMz，1H)，7.21-7.24(m，1H)，7.27-7.38(m，9H).
13C?NMR(100MHz，CDCl
3)：δ＝28.4，79.8，126.6，127.0，127.6，127.7，128.6，128.8，129.7，131.0，136.6，141.4，155.0.HRMS-ESI：Calcd.For?C
20H
23NNaO
2[M+Na]
+：332.1621.Found：332.1624.
Embodiment 88:
Under 80 ℃, will be to methyl benzenesulfonamide (1.5mmol, 256.5mg) and benzhydrol (0.5mmol, 92.0mg) and [BsTdmim] OTf (10mol%, 27.5mg), 1,4-dioxane 2.0mL places dry reaction flask, magnetic agitation reaction 3h.After reaction finishes, add secondary deionized water 10mL, then centrifugal.Product is washed three times with secondary deionized water, and water layer merges, and decompression is spin-dried for, 80 ℃ of lower vacuum-drying 24h, and ionic liquid carries out next step and recycles.The product recrystallization obtains sterling N-diphenyl-methyl-4-methyl benzenesulfonamide 156.7mg, and productive rate is that 93%, NMR data are with embodiment 1.After ionic liquid recycles 5 times, do not find that yield obviously descends.Specifically see Table 1.
Table 1
Claims (9)
1. the method for a functionalized ion liquid catalytically synthesizing aminated compounds, it is characterized in that: use sulfonamides, amides, phenyl amines, amino formate or nitrogen heterocyclic ring compounds, with alcohol compound as initial reactant, as catalyzer, wherein the cationic moiety of functionalized ion liquid is selected from glyoxaline cation, pyridylium, morpholine positively charged ion, tetramethyleneimine positively charged ion, guanidine cationoid, quaternary alkylphosphonium salt cationoid, two morpholine positively charged ion, two tetramethyleneimine positively charged ion or two glyoxaline cation with functionalized ion liquid; Anionicsite is selected from the tosic acid root; 25～150 ℃ of temperature of reaction, reaction times 0.1～48h, the derivative that the N-alkylated reaction generates corresponding amides class, sulfonamides, phenyl amines, amino formate compounds occurs with alcohol in amine.
2. the method for claim 1 is characterized in that catalyzer is a kind of in the following description:
Wherein R represents butyl or phenyl, and X-represents tosic acid root (TsO
-), tetrafluoroborate (BF
4 -), hexafluoro-phosphate radical (PF
6-), bisulfate ion (HSO
4 -), methanesulfonic root (CH
3SO
3 -) or camphorsulfonic acid root (CMs
-), n represents 1～18 integer.
3. the method for claim 1 is characterized in that sulfamide compound is selected from 4-methyl benzenesulfonamide, 4-nitrobenzene sulfonamide, benzsulfamide or amsacrine.
4. the method for claim 1 is characterized in that amides is selected from 4-methyl benzamide, 4-chlorobenzamide, benzamide, oxazolidine-2-ketone, methane amide, ethanamide, propionic acid amide, acrylamide, pyrrolidin-2-one, hexanolactam or picolinamide.
5. the method for claim 1 is characterized in that amino benzenes compounds is selected from 4-N-methyl-p-nitroaniline, 2-N-methyl-p-nitroaniline or 4-5-trifluoromethylaniline.
6. the method for claim 1 is characterized in that nitrogen-containing heterocycle compound is selected from 1H-pyrazoles, 4H-1,2,4-triazole, benzotriazole or 5-phenyl-1H-tetrazole.
7. the method for claim 1, it is characterized in that alcohol compound is selected from methyl alcohol, ethanol, chloroethanol, Virahol, hexalin, 1-phenylethyl alcohol, (E)-1,3-phenylbenzene-2-propylene-1-alcohol, 1,3-phenylbenzene-2-propine-1-alcohol, 2-methyl isophthalic acid-phenyl-2-propylene-1-alcohol, vinyl carbinol, styryl carbinol, benzhydrol, 4-methyldiphenyl methyl alcohol, 4-chlorodiphenyl methyl alcohol or 2-chlorodiphenyl methyl alcohol.
8. the method for claim 1 is characterized in that amine and the mol ratio of alcohol are 1: 1～5: 1.
9. the method for claim 1 is characterized in that reaction solvent is selected from Isosorbide-5-Nitrae-dioxane, Nitromethane 99Min., ether, toluene, acetonitrile, methylene dichloride, tetrahydrofuran (THF), DMF, [Bmim] [BF
4], [Bmim] [PF
6], methyl-sulphoxide, PEG-4000,1,2-ethylene dichloride, hexanaphthene, normal hexane, trichloromethane, tetracol phenixin, sym.-tetrachloroethane, methyl iso-butyl ketone (MIBK) or dimethylbenzene.
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