阅读说明：本技术 一种离子液体催化制备氧杂环化合物的新方法 (Novel method for preparing oxygen heterocyclic compound by ionic liquid catalysis ) 是由 刘志敏 王欢 赵燕飞 韩布兴 于 2020-04-13 设计创作，主要内容包括：本发明公开了一种离子液体催化制备氧杂环化合物的新方法。本发明提供的离子液体催化体系具有高效、简单、反应条件温和、无金属参与、无副产物、分离简单等优点,能高效催化脂肪二醚复分解环化制备氧杂环化合物,具有很强的工业应用价值。(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.)

1. The ionic liquid is used as a catalyst in the preparation of an oxygen heterocyclic compound.

2. Use according to claim 1, characterized in that: in the step of preparing the oxygen heterocyclic compound, the substrate is a fatty diether compound or a fatty diether analogue;

the reaction carried out is a metathesis reaction.

3. 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.

4. Use or method according to any of claims 1-3, characterized in that: 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.

5. Use or method according to any of claims 1-4, characterized in that: 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.

6. The use or method according to any one of claims 1 to 5, wherein both the anion and the cation of said ionic liquid are capable of forming hydrogen bonds with the oxygen atom and α -hydrogen in said 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.

7. Use or method according to any of claims 1-6, wherein: 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 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.

8. Use or method according to any of claims 1-7, 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 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.

9. Use or method according to any of claims 1-8, 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.

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 the oxygen atom and the α -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.