CN112812045B - Onium salt organic catalyst and preparation method and application thereof - Google Patents

Onium salt organic catalyst and preparation method and application thereof Download PDF

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CN112812045B
CN112812045B CN201911121050.4A CN201911121050A CN112812045B CN 112812045 B CN112812045 B CN 112812045B CN 201911121050 A CN201911121050 A CN 201911121050A CN 112812045 B CN112812045 B CN 112812045B
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伍广朋
郑煜佳
杨贯文
李博
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Zhejiang University ZJU
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Abstract

The invention discloses an onium salt organic catalyst, which has a structure shown in a formula (I), wherein L is a urea or thiourea group; m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000. The invention also discloses a preparation method of the onium salt organic catalyst, which comprises the following steps: any one of the reaction raw materials W 1 And any one of the reaction materials W 2 Mixing in solutionStirring for 1-500 hours at room temperature, and removing impurities and organic solvent to obtain the onium salt organic catalyst. The invention also discloses application of the onium salt organic catalyst in preparation of organic micromolecule and macromolecular polymers. The onium salt organic catalyst provided by the invention has the advantages of easy weighing, high catalytic activity, controllable reaction and the like; the preparation method provided by the invention is simple and high in yield.
Figure DDA0002275480280000011

Description

Onium salt organic catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to development and application of an organic catalyst for preparing organic small-molecule fine chemicals and high-molecular polymer materials.
Background
Compared with metal catalysts, the organic catalyst has the advantages of simple synthesis, low price and low biological toxicity. The most widely studied organic catalysts at present include heterocyclic carbenes (NHC), N-heterocyclic bases (NHCB), hindered Lewis pairs (FLP), tetrahydroammonium oxides/onium salts (PTC), polyphenols, fluoroalcohols, silanediols with co-catalysts, and Ionic Liquids (ILs), among others. The catalytic reaction by hydrogen bond has the advantages of simple and easy operation, such as alcohol, polyphenol, carboxylic acid, silanediol, fang Xianan, thiourea and the like which have been reported recently and are the most widely researched hydrogen bond catalysts. Among them, thiourea or urea is considered to have specific advantages in the aspects of toxicity, sustainability and milder conditions of use, and has the advantages of high catalytic activity, simple preparation, easy modulation of structure and the like.
Although urea and thiourea have good hydrogen bonding effect, urea or thiourea alone often cannot achieve good catalytic efficiency, and quaternary ammonium salt, organic base and the like are generally needed to be used as co-catalysts to form a high-efficiency catalytic system. Recently, a new type of two-component catalyst consisting of strong base and weak acid of urea and thiourea showing high efficiency, controllability and good chemical selectivity in the ring-opening polymerization of lactones has been reported in [ nat. Chem.2016,8,1047-1053]. By using urea and thiourea as hydrogen bond donor to change strong alkali (such as alkoxide of sodium/potassium), a new dual-component catalyst with higher activity can be preparedAgents [ j.am.chem.soc.2017,139,1645-1652; macromolecules 2018,51,2048-2053]. Similar to urea and thiourea, kleij Et al use TEAB (Et 4N) + Br - ) And aromatic amide as a two-component catalytic system realizes the fixation of carbon dioxide under the pressure of 10-30bar, and cyclic carbonate (ACS Catal.2017,7,3532) with high yield is obtained]。
In recent years, the preparation of the organic catalyst containing double functions in the same molecule by intramolecular combination of urea or thiourea and nucleophilic groups has more obvious advantages. For example, werner et al developed a series of bifunctional ammonium and phosphonium salts for catalyzing the cycloaddition of carbon dioxide and epoxides [ chemcat chem.2015,7,459] to produce various cyclic carbonate compounds. Inspired by urea or thiourea catalysts, toda and Shirakawa introduce urea-like groups and quaternary phosphonium salts into one molecule to prepare bifunctional catalysts that can efficiently synthesize cyclic carbonates [ ACS cat.2016, 6,6906; green chem.2016,18,4611].
In conclusion, the bifunctional organic catalyst has a synergistic effect of hydrogen bond activation and nucleophilic attack, has a good effect on various organic reactions such as the synthesis of cyclic carbonate by the activation and fixation of carbon dioxide, and shows more excellent performance. Unfortunately, the catalyst has the problems of complex preparation, low activity, difficult structure regulation and the like.
Disclosure of Invention
The invention provides a preparation method of an onium salt organic catalyst, which is simple and has high yield; the invention also provides the application of the onium salt organic catalyst in the preparation of fine chemicals with high added value.
The technical scheme provided by the invention is as follows:
an onium salt organic catalyst having a structure represented by formula (I):
Figure BDA0002275480260000021
wherein L is a urea or thiourea group; m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000;
when y =1, K is selected from any C which is unsubstituted or has a substituent 3 -C 18 Alkyl radical, C 3 -C 18 Cycloalkyl radical, C 3 -C 18 Alkenyl radical, C 3 -C 18 Alkynyl, C 7 -C 18 Aryl radical, C 3 -C 18 Heterocyclic radicals or C 7 -C 18 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;
when y is an integer of 2 or more, K is selected from unsubstituted or substituted C 1 -C 18 Alkyl radical, C 3 -C 18 Cycloalkyl radical, C 3 -C 18 Alkenyl, C3-C 18 Alkynyl, C 6 -C 18 Aryl radical, C 3 -C 18 Heterocyclyl or C 5 -C 18 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
Preferably, the structural formula of L is shown in formula (II):
Figure BDA0002275480260000031
wherein R is 1 、R 3 、R 4 Each independently selected from H, unsubstituted, substituted or containing one or at least one of O, S, N, si, P atomsTwo combinations of the following groups: c 1 -C 18 Alkyl radical, C 3 -C 18 Cycloalkyl, C 3 -C 18 Alkenyl, C3-C 18 Alkynyl, C 6 -C 18 Aryl radical, C 3 -C 18 Heterocyclyl or C 5 -C 18 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms; r 2 Is O or S;
Figure BDA0002275480260000032
denoted as a connecting bond.
Preferably, M is selected from one or a combination of at least two of the following structural formulae:
Figure BDA0002275480260000033
Figure BDA0002275480260000041
Figure BDA0002275480260000051
Figure BDA0002275480260000061
wherein R is 5 -R 38 Each independently selected from H, unsubstituted or substituted C 1 -C 18 Alkyl radical, C 3 -C 18 Cycloalkyl radical, C 3 -C 18 Alkenyl, C3-C 18 Alkynyl, C 6 -C 18 Aryl radical, C 3 -C 18 Heterocyclyl or C 5 -C 18 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight-chain alkyl with 1 to 10 carbon atoms, branched or straight-chain alkoxy with 1 to 10 carbon atoms, branched or straight-chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;
x represents a negative ion selected from F – 、Cl – 、Br – 、I – 、NO 3 – 、CH 3 COO – 、CCl 3 COO – 、CF 3 COO – 、ClO 4 – 、BF 4 – 、BPh 4 – 、N 3 – 、OH – One or a combination of at least two of p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2,4-dinitrophenol oxygen, 3,5-dinitrophenol oxygen, 2,4,6-trinitrophenol oxygen, 3,5-dichlorophenol oxygen, carbonate, bicarbonate, 3,5-difluorophenol oxygen, 3,5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen anion;
each R 5 -R 38 Any of the groups in (1) may be bonded to each other to form a ring.
Further preferably, the onium salt organic catalyst is:
Figure BDA0002275480260000071
the invention also provides a preparation method of the onium salt organic catalyst, which comprises the following steps: any one of the reaction raw materials W 1 And any one of the reaction materials W 2 Mixing and stirring the mixture in the solution, and removing impurities and organic solvent after stirring the mixture for 1 to 500 hours at room temperature to obtain an onium salt organic catalyst; the reaction raw material W 1 And W 2 Respectively as follows:
Figure BDA0002275480260000081
wherein R is 0 Is a sulfur atom or an oxygen atom; r' 1 、R’ 2 、R’ 3 Each independently selected from H, unsubstituted or substituted C 1 -C 18 Alkyl radical, C 3 -C 18 Cycloalkyl, C 3 -C 18 Alkenyl, C3-C 18 Alkynyl, C 6 -C 18 Aryl radical, C 3 -C 18 Heterocyclyl or C 5 -C 18 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;
m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000.
Wherein the organic solvent is one or more selected from tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1,4-dioxane or pyridine.
The reaction equation involved in the above preparation method is as follows:
Figure BDA0002275480260000082
the invention also provides the application of the onium salt organic catalyst in preparing organic micromolecules and macromolecular polymers, wherein one or at least two cyclic monomers are subjected to bulk polymerization under the contact of the organic catalyst to obtain the macromolecular polymers; one or more cyclic monomers react with carbon dioxide, carbon disulfide, carbon oxysulfide or carbon monoxide in the presence of an onium salt organic catalyst to obtain cyclic carbonate, cyclic lactone, a cyclic thiocarbonate small molecular compound and a macromolecular polymer.
Preferably, the cyclic monomer is selected from any one or more of the following structural formulae:
Figure BDA0002275480260000091
Figure BDA0002275480260000101
the onium salt organic catalyst provided by the invention is a bifunctional organic catalyst containing urea or thiourea and an onium salt, and has the advantages of easiness in weighing, high catalytic activity, reaction controllability (catalytic efficiency and yield are regulated and controlled by changing catalyst concentration, reactant concentration, reaction time, reaction temperature and the like) and the like when being used as the catalyst. The preparation method provided by the invention has the advantages of simple preparation, high yield, low consumption, low cost and the like. The onium salt organic catalyst provided by the invention can be used for effectively synthesizing fine chemicals with high added value, such as cyclic carbonate, thio-cyclic carbonate lactone and the like.
Drawings
FIG. 1 is a digital photograph of onium salt organic catalysts prepared in examples 1-5;
FIG. 2 is a nuclear magnetic resonance image of the onium salt organic catalyst prepared in example 2.
Detailed Description
The invention is described in detail below by way of specific examples:
alkylene oxides and abbreviations therefor
Figure BDA0002275480260000111
Cyclic lactone and its abbreviation
Figure BDA0002275480260000112
Example 1
Figure BDA0002275480260000113
(1) Adding 1mmol of A into a 100mL round-bottom flask, adding 10mL of dichloromethane, stirring to dissolve, adding 1mmol of phenyl isothiocyanate, stirring at room temperature overnight, draining to remove dichloromethane, settling the obtained residue with diethyl ether for several times to remove impurities, and drying to obtain B with yield of 83%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(2) Adding 1mmol B into 100mL round bottom flask, adding 10mL acetonitrile, adding 1mmol benzyl bromide, stirring at room temperature overnight, draining to remove acetonitrile, precipitating with ethyl acetate for multiple times to remove impurities, and drying to obtain onium salt organic catalyst (catalyst 1) with yield of 87%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
Example 2
Figure BDA0002275480260000121
(1) Adding 1mmol C into a 100mL round-bottom flask, adding 10mL dichloromethane, stirring to dissolve, adding 1mmol phenyl isothiocyanate, stirring at room temperature overnight, draining to remove dichloromethane, settling the obtained residue with diethyl ether for several times to remove impurities, and drying to obtain D with yield of 85%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(2) 1mmol D was added to a 100mL round bottom flask, 10mL acetonitrile was added thereto, 1.3mmol iodomethane and 1.5mmol potassium carbonate were added, the mixture was stirred at 60 ℃ overnight, the acetonitrile was removed by suction drying, impurities were removed by multiple sedimentation with ether, and drying was carried out to obtain an onium salt organic catalyst (catalyst 2) with a yield of 95%, which was characterized by nuclear magnetism as shown in FIG. 2 (deuterated reagent: deuterated chloroform CDCl) 3 )。
Example 3
Figure BDA0002275480260000131
(1) Adding 1mmol E into a 100mL round-bottom flask, adding 50mL methanol, adding 1mL triethylamine and 1mmol benzaldehyde at low temperature, stirring for reaction for 0.5h, and adding 2mmol NaBH in portions at low temperature 4 The reaction was stirred for 1h. The resulting solution was neutralized with 4mol/L hydrochloric acid (5 ml) and extracted with diethyl ether, the ether phase was discarded and the aqueous phase was treated with solid NaHCO 3 Neutralizing, extracting with ethyl acetate, draining to remove ethyl acetate, drying to obtain F with yield of 43%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(2) Adding 1mmol F into 100mL pressure bottle, adding 20mL acetonitrile, 1.5mmol potassium carbonate solid and 2.2mmol methyl iodide, stirring at 50 deg.C for 2 days, filtering to remove potassium carbonate, draining to remove acetonitrile, precipitating with diethyl ether for several times to remove impurities, drying to obtain G with yield of 73%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(3) To a 100mL round bottom flask was added 1mmol G, to which was added 10mL dichloromethane, stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature, and the reaction was stirred for 2h. Removing dichloromethane by pumping, precipitating with diethyl ether for multiple times to remove impurities, adding 10mL dichloromethane, adding excess triethylamine and 2mmol phenyl isothiocyanate, stirring for reaction overnight, precipitating with ethyl acetate for multiple times to remove impurities, and drying to obtain onium salt organic catalyst (catalyst 3) with yield of 74%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
Example 4
Figure BDA0002275480260000141
(1) Adding 1mmol diethylamine into 100mL pressure bottle, adding 10mL acetonitrile and 1.5mmol potassium carbonate solid, adding 2.5mmol I, stirring at 50 deg.C for 2 days, filtering to remove potassium carbonatePumping to remove acetonitrile, precipitating with diethyl ether for several times to remove impurities, and drying to obtain J with yield of 37%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(2) 1mmol J was added to a 100mL round bottom flask, 10mL dichloromethane was added thereto, stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature, and the reaction was stirred for 2h. The dichloromethane was removed by suction drying, the impurities were removed by multiple sedimentation with diethyl ether, 10mL of dichloromethane was added, excess triethylamine and 2mmol of phenylisothiocyanate were added, the reaction was stirred overnight, the impurities were removed by multiple sedimentation with diethyl ether, and drying was carried out to obtain the onium salt organic catalyst (catalyst 4) in a yield of 62%, which was characterized by nuclear magnetism (deuterated reagent: deuterated dimethyl sulfoxide DMSO-d 6).
Example 5
Figure BDA0002275480260000142
(1) Adding 1mmol piperidine into 100mL pressure bottle, adding 10mL acetonitrile and 1.5mmol potassium carbonate solid, adding 2.5mmol I, stirring at 50 deg.C for 2 days, filtering to remove potassium carbonate, draining to remove acetonitrile, precipitating with diethyl ether for several times to remove impurities, drying to obtain K with yield of 40%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl) 3 )。
(2) To a 100mL round bottom flask was added 1mmol K, to which was added 10mL dichloromethane, stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature, and the reaction stirred for 2h. The dichloromethane was removed by suction, the impurities were removed by multiple sedimentation with diethyl ether, 10mL of dichloromethane, excess triethylamine and 2mmol of phenylisothiocyanate were added thereto, the mixture was stirred overnight, the impurities were removed by multiple sedimentation with diethyl ether, and drying was carried out to obtain an onium salt organic catalyst (catalyst 5) with a yield of 58%, which was characterized by nuclear magnetism (deuterated reagent: deuterated dimethyl sulfoxide DMSO-d 6).
Digital photographs of catalysts 1-5 prepared in examples 1-5, respectively, are shown in fig. 1.
Application examples 1 to 13: method for catalyzing epoxyalkane to open ring to generate cyclic carbonate by using catalysts 1-5
Figure BDA0002275480260000151
The catalyst prepared in example 1-5 (0.07 mmol) was charged into an autoclave, and 35mmol of alkylene oxide was added and charged with 1.2MPa of CO 2 And reacting for 20 hours under the given temperature condition. Then releasing carbon dioxide, and taking nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer. The catalytic results and characterization are shown in table 1.
Table 1 test results of catalytic products of application examples 1-13
Figure BDA0002275480260000152
Application examples 14 to 18: catalyst 3 for catalytic homopolymerization of cyclic lactone
Figure BDA0002275480260000161
In a glove box, catalyst 3 (0.01 mmol) prepared in example 3 was taken and added to a serum bottle, and cyclic lactone (0.01 mol), 1ml of toluene, reacted at 80 ℃ for 6h. And (3) taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polyester. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 2.
TABLE 2 test results of the polymerization products of application examples 14 to 18
Figure BDA0002275480260000162
a M n Number average molecular weight, as determined by gel permeation chromatography; b molecular weight distribution (PDI) measured by gel permeation chromatography.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (2)

1. An onium salt organic catalyst, wherein the onium salt organic catalyst is:
Figure 171169DEST_PATH_IMAGE001
、
Figure 432518DEST_PATH_IMAGE002
、
Figure 576970DEST_PATH_IMAGE003
、
Figure 581967DEST_PATH_IMAGE004
or
Figure 740547DEST_PATH_IMAGE005
。
2. A process for preparing the onium salt organic catalyst of claim 1, wherein said process comprises: any one of the reaction raw materials W 1 And any one of the reaction materials W 2 Mixing and stirring in the solution, and after stirring for 1 to 500 hours at room temperature, removing impurities and an organic solvent to obtain an onium salt organic catalyst; the reaction raw material W 1 And W 2 Respectively as follows:
Figure 422064DEST_PATH_IMAGE006
、
Figure 236567DEST_PATH_IMAGE007
；
wherein R is 0 Is a sulfur atom or an oxygen atom; r' 1 、R’ 2 、R’ 3 Each independently selected from H, C 6 -C 18 An aromatic group;
m is an onium salt structure with a charge; y is any integer between 1 and 100000; z is any integer between 1 and 100000;
when y =1, K is selected from unsubstituted C 3 -C 18 An alkyl group;
when y is an integer of 2 or more, K is selected from unsubstituted C 1 -C 18 An alkyl group.
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