CN111440132B - Novel method for preparing oxygen heterocyclic compound by ionic liquid catalysis - Google Patents
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Abstract
The invention discloses a novel method for preparing an oxygen heterocyclic compound by ionic liquid catalysis. The ionic liquid catalytic system provided by the invention has the advantages of high efficiency, simplicity, mild reaction conditions, no metal participation, no by-product, simple separation and the like, can efficiently catalyze double decomposition and cyclization of fatty diether to prepare an oxygen heterocyclic compound, and has strong industrial application value.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a novel method for preparing an oxygen heterocyclic compound by ionic liquid catalysis.
Background
Oxygen heterocyclic compounds such as tetrahydrofuran, tetrahydropyran and the like and derivatives thereof are important chemicals and have wide application in chemical production. Such compounds are obtained by metathesis of aliphatic diethers of formula (1). However, the catalytic systems used at present are predominantly metal Lewis acid catalysts, e.g. Fe (OTf)3、AlCl3、FeCl3、FeBr3And the like. Has the defects of low reaction efficiency, low selectivity of target products, difficult separation, metal residue and the like. In order to meet the requirements of green and sustainable development, the development of a new method for preparing the oxygen heterocyclic compound by the double decomposition reaction of the aliphatic diether which is green, simple, efficient and free of metal participation is of great significance.
The ionic liquid consists of organic cations and inorganic/organic anions, has high designability, and can be endowed with special functions through the functional design of the anions and the cations, so that the ionic liquid is applied to various fields and shows wide application prospects. In particular, various interactions in the ionic liquid system are coupled, so that the catalytic chemical reaction can be realized under the condition of no metal, the unique performance is shown, and the development opportunity is provided for a novel catalytic system and a novel chemical reaction method. Under the condition of no metal, researches and technologies for preparing oxygen heterocyclic compounds such as tetrahydrofuran, tetrahydropyran and the like and derivatives thereof by catalyzing aliphatic diether with ionic liquid are not reported.
Disclosure of Invention
The invention aims to provide a novel method for preparing an oxygen heterocyclic compound by using ionic liquid to catalyze fatty diether metathesis under mild conditions.
The invention claims an application of ionic liquid as a catalyst in preparation of an oxygen heterocyclic compound.
Specifically, in the step of preparing the heterocyclic oxygen compound by the above application, the substrate is a fatty diether compound or a fatty diether analogue;
the reaction carried out is a metathesis reaction.
The present invention also claims a method of preparing an heterocyclic oxygen compound, the method comprising: taking a fatty diether compound or a fatty diether analogue as a substrate to carry out reaction; the method is characterized in that: the catalyst used in the reaction is ionic liquid; the reaction is a metathesis reaction.
Specifically, in the reaction step, the temperature is 50-200 ℃; in particular 120-150 ℃ or 140 ℃;
the time is 12-36 h; in particular 10h-24 h.
The feeding molar ratio of the substrate to the ionic liquid is 1: 0.1-1; specifically 1:0.1-1:0.5 or 1: 0.2.
Both the anion and the cation of the ionic liquid are capable of forming hydrogen bonds with oxygen atoms and alpha-hydrogen in the substrate;
specifically, the ionic liquid is at least one selected from the group consisting of [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-propylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-pyridine ] trifluoromethanesulfonate, [ 1-propylsulfonic acid group-2, 3-dimethylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-2, 3-methylimidazole ] trifluoromethylacetate, [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethylacetate and [ 1-butylsulfonic acid group-3-methylimidazole ] hydrogen sulfate.
The structural formula of the ionic liquid is shown as follows:
the fatty diether compound is selected from at least one of dialkoxyalkanes and dialkoxyarylalkanes;
in the dialkoxy alkane, the carbon number of the alkane is specifically 2-6; specifically 4 or 5; more specifically at least one selected from the group consisting of 1, 4-dimethoxybutane, 1, 5-dimethoxypentane, 1, 5-diethyloxypentane, 1, 5-dipropoxypentane and 1, 5-dibutoxypentane;
in the dialkoxyarylalkanes, aryl is specifically phenyl or substituted phenyl; the alkane has a carbon number of 3-6; specifically 4 or 5; in the substituted phenyl, the substituent is specifically selected from at least one of C1-C5 alkyl and halogen; the alkyl of C1-C5 is methyl or ethyl;
the dialkyloxyarylalkanes are selected in particular from at least one of 1, 4-dimethoxy-2-phenylbutane, 1, 5-dimethoxy-2-phenylpentane, 1, 5-dimethoxy-3-p-tolylpentane, 1, 5-dimethoxy-3-p-chlorophenylpentane, 1, 5-dimethoxy-2, 2-dimethyl-3-phenylpentane, 1, 4-dimethoxy-1, 4-dimethyl-butane and 1, 4-dimethoxy-1-methylbutane;
the structural formula of the fatty diether compound is shown as follows:
the fatty diether analog is a dialkyl oxysulfonamide; in particular dialkoxyaryl sulfonamides; more particularly N, N-bis (2-methoxyethyl) -4-tolylsulfonamide or N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide.
The structural formula of the above N, N-bis (2-methoxyethyl) -4-tolylsulfonamide or N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide is shown below:
the oxygen heterocyclic compound is at least one of tetrahydrofuran, tetrahydrofuran derivatives, tetrahydropyran derivatives, 1, 4-dioxane and benzenesulfonyl morpholine compounds;
the tetrahydrofuran derivative is alkyl or aryl substituted tetrahydrofuran; the alkyl is C1-C4 alkyl; more specifically methyl; the aryl is in particular phenyl;
the tetrahydrofuran derivative is at least one selected from 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 2-phenyltetrahydrofuran and 3-phenyltetrahydrofuran;
the tetrahydropyran derivative is aryl-substituted tetrahydropyran; the aryl is particularly phenyl or substituted phenyl; in the substituted phenyl, the substituent is selected from at least one of halogen and alkyl; the alkyl is C1-C4 alkyl; more specifically methyl; the aryl is in particular phenyl; the halogen is in particular chlorine;
the tetrahydropyran derivative is specifically selected from at least one of 2-phenyltetrahydropyran, 3-p-phenylmethyltetrahydropyran, 4-phenyltetrahydrofuran, 4-p-tolyltetrahydropyran, 3-p-chlorophenyltetrahydropyran, 4-p-chlorophenyltetrahydropyran, 2-dimethyl-3-phenyltetrahydropyran and 3, 3-dimethyl-4-phenyltetrahydropyran;
the benzenesulfonyl morpholine compounds are selected from at least one of 4-toluenesulfonyl morpholine and 4-nitrobenzenesulfonylmorpholine.
The structural formula of the oxygen heterocyclic compound is shown as follows:
the method further comprises the following steps: and after the reaction is finished, carrying out phase separation on the reaction system to obtain the oxygen heterocyclic compound.
Specifically, the phase separation comprises: after the reaction system was immersed in ice water to terminate the reaction, the reaction system was allowed to stand at room temperature, the reaction mixture was placed in a separatory funnel and divided into upper and lower layers, and the upper organic phase was taken.
The ionic liquid catalytic system provided by the invention has the advantages of high efficiency, simplicity, mild reaction conditions, no metal participation, no by-product, simple separation and the like, can efficiently catalyze double decomposition and cyclization of fatty diether to prepare an oxygen heterocyclic compound, and has strong industrial application value.
Detailed Description
The method of the present invention is described below with reference to specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
EXAMPLE 1 preparation of tetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-butylsulfonic acid-3-methylimidazole]Triflate ([ SO ]3H-BMIm][OTf]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 15 hours; immersing the reaction kettle in ice waterThe reaction was terminated and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 94%, the product was tetrahydropyran, and the isolation yield thereof was 94%.
For reaction products1H and13c, determining the structure by using a nuclear magnetic spectrum:
1H NMR(400MHz,DMSO)δ7.68–7.62(m,2H),7.55(d,J＝7.4Hz,1H),7.49(t,J＝7.4Hz,2H)。
13C NMR(101MHz,DMSO)δ154.81,133.07,131.36,129.50,119.53,119.51,85.03,81.68。
from the above, the product has a correct structure and is tetrahydropyran.
EXAMPLE 2 preparation of tetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxypentane
0.1mol of 1, 5-dimethoxypentane and 0.1mol of ionic liquid [ SO3H-BMIm][OTf]Placing the mixture in a 50 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. Determining the conversion rate of the raw material according to the analysis result>99.9% of tetrahydropyran as product, isolated in yield>99％。
EXAMPLE 3 preparation of tetrahydropyran by [ 1-propylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-propylsulfonic acid-3-methylimidazole]Triflate ([ SO ]3H-PrMIm][OTf]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Get the upper layer ofOrganic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 90%, the product was tetrahydropyran, and the isolation yield thereof was determined to be 90%.
EXAMPLE 4 preparation of tetrahydropyran by [ 1-butylsulfonylpyridine ] triflate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-butylsulfonic pyridine ]]Triflate ([ SO ]3H-BPy][OTf]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, it was determined that the conversion of the raw material was 92%, the product was tetrahydropyran, and the isolation yield thereof was 92%.
EXAMPLE 5 preparation of tetrahydropyran by [ 1-butylsulfonic acid-2, 3-dimethylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-butylsulfonic acid-2, 3-dimethylimidazole]Triflate ([ SO ]3H-BMMIm][OTf]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, it was determined that the conversion of the raw material was 80%, the product was tetrahydropyran, and the isolation yield thereof was 80%.
EXAMPLE 6 preparation of tetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethylacetate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-butylsulfonic acid-3-methylimidazole]Trifluoromethyl acetate ([ SO)3H-BMIm][TA]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; move toHeating in oil bath at 150 deg.c while stirring for 10 hr; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, it was determined that the conversion of the raw material was 80%, the product was tetrahydropyran, and the isolation yield thereof was 80%.
EXAMPLE 7 preparation of tetrahydropyran by [ 1-butylsulfo-3-methylimidazole ] bisulfate catalysis of 1, 5-dimethoxypentane
2mmol of 1, 5-dimethoxypentane and 0.2mmol of ionic liquid [ 1-butylsulfonic acid-3-methylimidazole]Bisulfate ([ SO ]3H-BMIm][HSO4]) Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 140 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 85%, the product was tetrahydropyran, and the isolation yield thereof was 85%.
Example 8 preparation of tetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dipropoxypentane
1mmol of 1, 5-dipropoxypentane and 0.5mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 87%, the product was tetrahydropyran, and the isolation yield thereof was 87%.
Example 9 preparation of tetrahydropyran by [ 1-butylsulfo-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dibutoxypentane
1mmol of 1, 5-dibutoxypentane and 0.5mmol of ionLiquid [ SO3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 140 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 78%, the product was tetrahydropyran, and the isolation yield thereof was 78%.
EXAMPLE 10 preparation of 2-phenyltetrahydrofuran from 1, 4-dimethoxy-2-phenylbutane with [ 1-butylsulfanyl-3-methylimidazole ] trifluoromethanesulfonate
1mmol of 1, 4-dimethoxy-2-phenylbutane and 0.2mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. From the results of the analysis, the conversion of the raw material was determined to be>99% of the product was 2-phenyltetrahydrofuran, isolated in 99% yield.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.35–7.27(m,2H),7.27–7.17(m,3H),4.14(t,J＝8.0Hz,1H),4.06(td,J＝8.3,4.5Hz,1H),3.91(q,J＝7.9Hz,1H),3.72(t,J＝8.0Hz,1H),3.39(q,J＝8.0Hz,1H),2.39-2.31(m,1H),2.05–1.95(m,1H).
13C NMR(101MHz,CDCl3):δ/ppm＝142.68,128.57,127.23,126.48,74.65,68.50,45.01,34.65.
the nuclear magnetic data demonstrated that the product was 2-phenyltetrahydrofuran.
EXAMPLE 11 preparation of 2-phenyltetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxy-2-phenylpentane
1mmol of 1, 5-dimethoxy-2-phenylpentane and 0.2mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. From the results of the analysis, the conversion of the raw material was determined to be>99% and the product is 2-phenyltetrahydropyran, isolated in 99% yield.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.35–7.23(m,2H),7.2–7.18(m,3H),3.99–3.95(m,2H),3.50–3.31(m,2H),2.83(tt,J＝10.7,3.5Hz,1H),2.10–1.91(m,1H),1.72(dddt,J＝16.7,12.9,8.4,4.1Hz,3H).
13C NMR(101MHz,CDCl3):δ/ppm＝142.65,128.49,127.37,126.61,73.83,68.19,43.00,30.41,26.22.
the nuclear magnetic data confirmed that the product was 2-phenyltetrahydropyran.
EXAMPLE 12 preparation of 3-phenyltetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxy-3-phenylpentane
1mmol of 1, 5-dimethoxy-3-phenylpentane and 0.2mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. From the results of the analysis, the conversion of the raw material was determined to be>99% and the product is 3-phenyltetrahydropyran, isolated in 99% yield.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.24–7,20(m,2H),7.17c 7.06(m,3H),4.11–3.89(m,2H),3.43(td,J＝11.5,2.6Hz,2H),2.76–2.55(m,1H),1.78–1.65(m,4H).
13C NMR(101MHz,CDCl3):δ/ppm＝145.90,128.53,126.74,126.31,68.39,41.61,34.00.
the nuclear magnetic data confirmed that the product was 3-phenyltetrahydropyran.
EXAMPLE 13 preparation of 3-para-benzyltetrahydropyran by [ 1-butylsulfonic acid-3-methylimidazole ] trifluoromethanesulfonate catalysis of 1, 5-dimethoxy-3-para-benzylpentane
1mmol of 1, 5-dimethoxy-3-p-phenylmethyl pentane and 0.2mmol of ionic liquid [ SO3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. From the results of the analysis, the conversion of the raw material was determined to be>99% of the product, namely 3-p-phenylmethyl tetrahydropyran, and the isolation yield is 96%.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.03(s,4H),4.08–3.86(m,2H),3.42(td,J＝11.5,2.6Hz,2H),2.62(tt,J＝11.5,4.4Hz,1H),2.23(s,3H),1.76–1.62(m,4H).
13C NMR(101MHz,CDCl3):δ/ppm＝142.96,135.75,129.20,126.60,68.43,41.20,34.12,20.96.
the nuclear magnetic data confirmed that the product was 3-p-benzyltetrahydropyran.
EXAMPLE 14 preparation of 3-p-chlorophenyl tetrahydropyran by catalysis of 1, 5-dimethoxy-3-p-chlorophenyl pentane with [ 1-butylsulfo-3-methylimidazole ] trifluoromethanesulfonate
1mmol of 1, 5-dimethoxy-3-p-chlorophenyl pentane and 0.2mmol of ionic liquid [ SO3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion of the raw material was determined to be 84%, and the product was 3-p-chlorophenyl tetrahydropyran, which was isolated in a yield of 83%.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.34–7.12(m,2H),7.06(d,J＝8.2Hz,2H),4.10–3.86(m,2H),3.42(td,J＝11.2,3.3Hz,2H),2.64(m,1H),1.76–1.55(m,4H).
13C NMR(101MHz,CDCl3):δ/ppm＝144.33,131.85,128.57,128.07,68.17,40.96,33.86.
the nuclear magnetic data demonstrated that the product was 3-p-chlorophenyl tetrahydropyran.
EXAMPLE 15 preparation of 2, 2-dimethyl-3-phenyltetrahydropyran by catalysis of 1, 5-dimethoxy-2, 2-dimethyl-3-phenylpentane by [ 1-butylsulfo-3-methylimidazole ] trifluoromethanesulfonate
1mmol of 1, 5-dimethoxy-2, 2-dimethyl-3-phenylpentane and 0.5mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 10 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. From the results of the analysis, the conversion of the raw material was determined to be>99% of the product, 2-dimethyl-3-phenyltetrahydropyran, isolated in 98% yield.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.24–7.16(m,2H),7.16–7.10(m,1H),7.08–7.06(m,2H),4.03(ddt,J＝11.2,4.8,1.2Hz,1H),3.50–3.44(m,1H),3.44–3.35(m,1H),3.19–3.13(m,1H),2.48(dd,J＝13.0,3.6Hz,1H),2.28–2.12(m,1H),1.47–1.31(m,1H),0.83(s,3H),0.61(s,3H).
13C NMR(101MHz,CDCl3):δ/ppm＝141.72,129.18,127.68,126.37,80.17,69.17,51.34,34.70,28.04,25.00,18.86.
the nuclear magnetic data confirmed that the product was 2, 2-dimethyl-3-phenyltetrahydropyran.
EXAMPLE 16 preparation of 4-tosylmorpholine by catalysis of N, N-bis (2-methoxyethyl) -4-tolylsulfonamide with [ 1-butylsulfonyl-3-methylimidazole ] trifluoromethanesulfonate
1mmol of N, N-bis (2-methoxyethyl) -4-tolylsulfonamide and 0.2mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 140 ℃, and stirring and heating the mixture for 24 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion rate of the raw material is determined to be 90%, the product is 4-tosylmorpholine, and the isolation yield is determined to be 90%.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝7.64(d,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),3.74–3.72(m,4H),2.99–2.96(m,4H),2.44(s.3H).
13C NMR(101MHz,CDCl3):δ/ppm＝143.93,132.13,129.73,127.88,66.09,45.99,21.50.
the nuclear magnetic data confirmed that the product was 4-tosylmorpholine.
EXAMPLE 17 preparation of 4-Nitrobenzenesulfonylmorpholine by catalysis of N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide with [ 1-butylsulfonyl-3-methylimidazole ] trifluoromethanesulfonate
1mmol of N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide and 0.1mmol of ionic liquid [ SO ]3H-BMIm][OTf]Placing the mixture in a 20 ml stainless steel reaction kettle, and sealing; moving the mixture into an oil bath at 120 ℃, and stirring and heating the mixture for 24 hours; the reaction vessel was immersed in ice water to terminate the reaction, and then left at room temperature for a while. The reaction solution was transferred to a separatory funnel and divided into upper and lower layers. Taking the upper organic phase, using1H and13c nuclear magnetic analysis of the composition and determination of the material structure. According to the analysis result, the conversion rate of the raw material is determined to be 84%, and the product is 4-nitrobenzeneSulfonylmorpholine, isolated in 84% yield.
The product nuclear magnetic data are as follows:
1H NMR(400MHz,CDCl3):δ/ppm＝8.48–8.37(m,2H),8.00–7.92(m,2H),3.92–3.67(m,4H),3.13–2.91(m,4H).
13C NMR(101MHz,CDCl3):δ/ppm＝150.37,141.43,128.96,124.40,66.01,45.91.
the nuclear magnetic data prove that the product is 4-nitrobenzenesulfonylmorpholine.
Claims (8)
1. The ionic liquid is used as a catalyst for preparing the oxygen heterocyclic compound;
in the step of preparing the oxygen heterocyclic compound, the substrate is a fatty diether compound or a fatty diether analogue;
the reaction is a double decomposition reaction;
the ionic liquid is selected from at least one of [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-propylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-pyridine ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-2, 3-dimethylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethylacetate and [ 1-butylsulfonic acid group-3-methylimidazole ] hydrogen sulfate;
the aliphatic diether compound is selected from 1, 4-dimethoxybutane, 1, 5-dimethoxypentane, 1, 5-diethyloxypentane, 1, 5-dipropoxypentane, 1, 5-dibutoxypentane, 1, 4-dimethoxy-2-phenylbutane, at least one of 1, 5-dimethoxy-2-phenylpentane, 1, 5-dimethoxy-3-p-tolylpentane, 1, 5-dimethoxy-3-p-chlorophenylpentane, 1, 5-dimethoxy-2, 2-dimethyl-3-phenylpentane, 1, 4-dimethoxy-1, 4-dimethyl-butane and 1, 4-dimethoxy-1-methylbutane;
the fatty diether analog is N, N-bis (2-methoxyethyl) -4-tolylsulfonamide or N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide.
2. A method of preparing an oxirane compound, comprising: taking a fatty diether compound or a fatty diether analogue as a substrate to carry out reaction; the method is characterized in that: the catalyst used in the reaction is ionic liquid; the reaction is a metathesis reaction;
the ionic liquid is selected from at least one of [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-propylsulfonic acid group-3-methylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-pyridine ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-2, 3-dimethylimidazole ] trifluoromethanesulfonate, [ 1-butylsulfonic acid group-3-methylimidazole ] trifluoromethylacetate and [ 1-butylsulfonic acid group-3-methylimidazole ] hydrogen sulfate;
the aliphatic diether compound is selected from 1, 4-dimethoxybutane, 1, 5-dimethoxypentane, 1, 5-diethyloxypentane, 1, 5-dipropoxypentane, 1, 5-dibutoxypentane, 1, 4-dimethoxy-2-phenylbutane, at least one of 1, 5-dimethoxy-2-phenylpentane, 1, 5-dimethoxy-3-p-tolylpentane, 1, 5-dimethoxy-3-p-chlorophenylpentane, 1, 5-dimethoxy-2, 2-dimethyl-3-phenylpentane, 1, 4-dimethoxy-1, 4-dimethyl-butane and 1, 4-dimethoxy-1-methylbutane;
the fatty diether analog is N, N-bis (2-methoxyethyl) -4-tolylsulfonamide or N, N-bis (2-methoxyethyl) -4-nitrophenylsulfonamide.
3. The method of claim 2, wherein: in the reaction step, the temperature is 50-200 ℃; the time is 12-36 h.
4. The method of claim 2, wherein: in the reaction step, the temperature is 120-150 ℃;
the time is 10-24 h.
5. The method according to any one of claims 2-4, wherein: the feeding molar ratio of the substrate to the ionic liquid is 1:0.1-1: 1.
6. The method of claim 5, wherein: the feeding molar ratio of the substrate to the ionic liquid is 1:0.1-1: 0.5.
7. The use according to claim 1 or the method according to any of claims 2-4, wherein: the oxygen heterocyclic compound is at least one of tetrahydrofuran, tetrahydrofuran derivatives, tetrahydropyran derivatives, 1, 4-dioxane and benzenesulfonyl morpholine compounds;
the tetrahydrofuran derivative is at least one selected from 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 2-phenyltetrahydrofuran and 3-phenyltetrahydrofuran;
the tetrahydropyran derivative is selected from at least one of 2-phenyl tetrahydropyran, 3-p-phenylmethyl tetrahydropyran, 4-phenyl tetrahydrofuran, 4-p-tolyl tetrahydropyran, 3-p-chlorophenyl tetrahydropyran, 4-p-chlorophenyl tetrahydropyran, 2-dimethyl-3-phenyl tetrahydropyran and 3, 3-dimethyl-4-phenyl tetrahydropyran;
the benzenesulfonyl morpholine compounds are selected from at least one of 4-toluenesulfonyl morpholine and 4-nitrobenzenesulfonylmorpholine.
8. The method according to any one of claims 2-4, wherein: the method further comprises the following steps: and after the reaction is finished, carrying out phase separation on the reaction system to obtain the oxygen heterocyclic compound.
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