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CN117430125A - Preparation method and application of manganese doped mesoporous structure-containing acidic Beta zeolite molecular sieve - Google Patents

Preparation method and application of manganese doped mesoporous structure-containing acidic Beta zeolite molecular sieve Download PDF

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CN117430125A
CN117430125A CN202311372178.4A CN202311372178A CN117430125A CN 117430125 A CN117430125 A CN 117430125A CN 202311372178 A CN202311372178 A CN 202311372178A CN 117430125 A CN117430125 A CN 117430125A
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cinnamic acid
molecular sieve
beta
sodium
manganese
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叶俊青
陈圣春
代燕子
孙中华
何明阳
陈群
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Changzhou University
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Abstract

The invention discloses a preparation method of an acidic Beta zeolite molecular sieve with a manganese doped mesoporous structure and application of the molecular sieve in catalyzing decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate to synthesize a vinyl sulfone compound. The invention adopts an in-situ doping hydrothermal method, takes silicic acid, sodium metaaluminate and manganese salt as raw materials, and adopts a quaternary ammonium salt template agentIn the presence of the mesoporous structure, the acid Beta zeolite molecular sieve with the specific surface area of 435-693 m is prepared 2 The ratio of silicon to aluminum is 20:1-60:1, and the crystallinity is 85-100%. Compared with the existing homogeneous manganese salt catalyst, the manganese doped acidic Beta molecular sieve containing a mesoporous structure has higher catalytic activity, good reusability and almost no metal loss in the process of catalyzing the decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate, and the yield of the vinyl sulfone compound prepared by catalysis is up to 95 percent, so that the method has good application prospect in the field of organic catalytic synthesis.

Description

Preparation method and application of manganese doped mesoporous structure-containing acidic Beta zeolite molecular sieve
Technical Field
The invention belongs to the field of organic catalytic synthesis, and particularly relates to a preparation method and application of an acidic Beta zeolite molecular sieve with a mesoporous structure doped with manganese.
Background
Vinyl sulfone compounds are an important class of organic molecules and are widely used in the fields of pharmaceutical chemistry, organic synthetic chemistry and the like. For example, vinyl sulfone compounds are important structural fragments in many drugs, such as cysteine protease inhibitors, membrane protein transpeptidase inhibitors, HIV-1 integrase inhibitors, and the like. Furthermore, they are also widely used as Michael acceptors and the like in organic synthesis.
Currently, there are various methods for synthesizing vinyl sulfone compounds, such as oxidation of vinyl sulfide, reduction of acetylene sulfone, condensation of aromatic aldehyde with sulfonylacetic acid, β elimination of seleno sulfone or halosulfone, coupling of alkenylboric acid with sodium benzene sulfinate, decarboxylation sulfonylation of cinnamic acid and its derivatives with sodium sulfinate, ring opening reaction of terminal epoxide with sodium sulfinate, and the like. Among them, the decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate to synthesize vinyl sulfone compound is considered as a most efficient and very promising synthesis method. Since the reactant cinnamic acid can be directly prepared from aromatic aldehyde through Perkin reaction, the molecular is easy to obtain, low in price and stable in structure, and the byproduct of the decarboxylation sulfonylation reaction is nontoxic CO 2 .2014Tan Ze et al, pd (OAc) using cinnamic acid and sodium benzene sulfinate as raw materials 2 And 1, 4-bis (diphenylphosphino) butane (dppb) as catalyst, ag 2 CO 3 As an additive, DMF was used as a solvent, and reacted at 75℃for 6 hours to give the product vinyl sulfone in 45-94% (R.Guo, Q.Gui, D.Wang, Z.Tan.Catal.Lett.,2014,144,1377-1383). Innovative of Hunan university, et al, mn (OAc) using derivatives of cinnamic acid and sodium benzene sulfinate as raw materials 2 As a catalyst, DMSO was used as a solvent, and the reaction was carried out at 110℃for 12 hours, with a yield of vinyl sulfone of 57-86% (N.Xue, R.Guo, X.Tu, W.Luo, W.Deng, J.Xiang.Synlett,2016,27,2695-2698). In addition, diacetoxyiodobenzene (PhI (OAc) 2 )、I 2 /TBHP、K 2 CO 3 Vinyl sulfones (P.Katrun, S.Hlekhlai, J.Meesin, M.Pohmakotr, V.Reutrakul, T.Jaipetch, D.Soorukram, C.Kuhakarn, org.Biomol.Chem.,2015,13,4785-4794; R.Singh, B.Allam, N.Singh, K.Kumari, S.Singh, K.Singh, org.Lett.,2015,17,2656-2659;Y.Xu,X.Tang,W.Hu,W.Wu,H.Jiang,Green Chem, 2014,16,3720-3723) may be synthesized by catalytic decarboxylation of sulfonyl groups.
However, all reported works adopt homogeneous catalysts, which have the problems of high cost, difficult recovery, high energy consumption, heavy metal pollution and the like, and do not meet the requirements of sustainable chemistry and green chemistry. Guo Cancheng et al used cinnamic acid and sodium benzene sulfinate as raw materials, cuO (20 mol%) as a catalyst, KI as an additive, DMSO as a solvent, and reaction at 100℃for 24 hours to obtain styryl sulfone with a yield of 74% by decarboxylation and sulfonylation, but the reaction time was long, the amount of catalyst used was large, and the yield of the product could not be further improved (Q.Jiang, X.Bin, J.Jiang, A.Zhao, Y.Zhao, Y.Li, N.He, C.Guo.J.Org.Chem.,2014,79,7372-7379). Therefore, the development of a heterogeneous catalyst which has high activity, low price and environment friendliness and can be recycled for efficiently catalyzing cinnamic acid and sodium benzene sulfinate to synthesize styryl sulfone has great significance.
The Beta zeolite molecular sieve has larger specific surface area, rich and ordered pore canal structure, high thermal stability and acid sites, is favorable for the adsorption and catalysis of reactants and the desorption of products, and is used as a green and environment-friendly heterogeneous catalysisThe catalyst is widely applied to various catalytic fields such as petrochemical industry, fine chemical industry, environmental protection and the like. The active metal Mn doped Beta molecular sieve catalyst not only has the advantages of Beta molecular sieve, but also increases the catalytic active sites by Mn ions introduced into the molecular sieve framework. Xia Qinghua et al prepared Mn-Beta molecular sieves by ion exchange and used to catalyze olefins with H 2 O 2 The catalyst has better catalytic performance on smaller-sized olefin or electron-rich terminal olefin, and still has higher catalytic activity after repeated recycling (B.Qi, X.Lu, D.Zhou, Q.Xia, Z.Tang, S.Fang, T.Pang, Y.Dong, J.Mol.Catal.A: chem.,2010,322,73-79). Zhang Guangxu et al prepared Mn/Beta molecular sieves by impregnation which selectively catalyzed the reduction of NO to N 2 The conversion of NO at 240 ℃ can be achieved up to 97.5% probably due to the higher surface Mn content and surface active oxygen groups and the appropriate content of weak acid sites favoring the reaction (W.Xu, G.Zhang, H.Chen, G.Zhang, Y.Han, Y.Chang, P.Gong, chinese j.catalyst., 2018,39,118-127). However, to date, application of Mn-doped acidic Beta zeolite molecular sieve containing mesoporous structure to catalyzing decarboxylation coupling reaction of cinnamic acid and sodium benzene sulfinate to synthesize styryl sulfone compound has not been reported in related literature.
Therefore, the manganese-containing mesoporous acid Beta molecular sieve which has high activity, good stability and recycling property is researched and developed, and has important scientific significance and application value when being used for efficiently catalyzing the decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate to synthesize the styryl compound.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the manganese doped acidic Beta zeolite molecular sieve with a mesoporous structure, which is characterized in that: the molecular sieve has a structure of Mn-nSi-Al-Beta, wherein n represents the molar ratio of Si/Al, and n=20-60;
the acidic Beta zeolite molecular sieve has a characteristic X-ray powder diffraction pattern as shown below:
wherein the X-ray powder diffraction pattern is based on a relative intensity scale, wherein the strongest line in the X-ray powder diffraction pattern is designated as the value 100, when the corresponding relative intensity is: w represents weak, i.e. 20 or less; m represents, i.e. > 20 to ∈40; s represents strong, i.e. > 40 to 60; and vs represents very strong, i.e. > 60.
As a preferred embodiment of the acidic Beta zeolite molecular sieve of the present invention, wherein: the specific surface area of the acidic Beta zeolite molecular sieve is 435-693 m 2 And/g, wherein the silicon-aluminum ratio is 20:1-60:1, and the crystallinity is 85-100%.
In order to solve the technical problems, the invention provides the following technical scheme: a process for preparing acidic zeolite Beta molecular sieve includes such steps as preparing zeolite Beta,
mixing silicic acid, manganese salt and deionized water uniformly, dropwise adding concentrated hydrochloric acid to adjust the pH to 1.0, then adding quaternary ammonium salt and sodium metaaluminate, stirring uniformly, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and crystallizing for a period of time at a constant temperature;
washing with deionized water and absolute ethyl alcohol, drying, and roasting at 550 ℃ for 5 hours to obtain the manganese doped acidic Beta molecular sieve catalyst M-Mn-Beta containing mesoporous structure.
As a preferred embodiment of the preparation process according to the invention, there is provided: the mass ratio of the silicic acid to the sodium metaaluminate is 20:1-60:1.
As a preferred embodiment of the preparation process according to the invention, there is provided: the quaternary ammonium salt is one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and hexadecyl trimethyl ammonium bromide, and each 1g of silicic acid corresponds to 1.2-3 g of quaternary ammonium salt; the manganese salt is one or a mixture of a plurality of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride, and each 1g of silicic acid corresponds to 0.03-0.1 g of manganese salt.
As a preferred embodiment of the preparation process according to the invention, there is provided: and crystallizing for a period of time at a constant temperature, wherein the crystallization temperature is 100-200 ℃ and the crystallization time is 5-15 days.
It is still another object of the present invention to overcome the deficiencies in the prior art and to provide an acidic zeolite Beta molecular sieve for use in a process for preparing the same, which comprises: the acidic Beta zeolite molecular sieve is applied to catalyzing the decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate to prepare a vinyl sulfone compound, wherein the preparation method comprises the steps of mixing cinnamic acid, sodium benzene sulfinate, an acidic Beta zeolite catalyst M-Mn-Beta, an additive and a solvent, and reacting for 1-24 hours at 50-150 ℃ to obtain the vinyl sulfone silicon compound.
As a preferred embodiment of the application according to the invention, wherein: the cinnamic acid is at least one of cinnamic acid and derivatives thereof, 2-methyl cinnamic acid, 3-methyl cinnamic acid, 2-ethoxy cinnamic acid, 4-methoxy cinnamic acid, 3-fluoro cinnamic acid, 4-fluoro cinnamic acid, 2, 4-difluoro cinnamic acid, 2-chloro cinnamic acid, 3-chloro cinnamic acid, 4-chloro cinnamic acid and 3-bromo cinnamic acid; the sodium benzene sulfinate is at least one of sodium benzene sulfinate and its derivatives, sodium 4-methyl benzene sulfinate, sodium 4-fluorobenzene sulfinate and sodium 4-chlorobenzene sulfinate; the mass ratio of cinnamic acid to sodium benzene sulfinate is 1:1-1:5; the addition amount of the acidic Beta molecular sieve catalyst M-Mn-Beta is 0.1 to 5mol percent of the amount of cinnamic acid substances.
As a preferred embodiment of the application according to the invention, wherein: the additive is KI, naI, NH 4 I、I 2 、K 2 CO 3 0.1-0.5 millimole of additive corresponding to 0.1 millimole of cinnamic acid in one of KCl and KBr; the solvent is dimethyl sulfoxide,One or more of N, N-dimethylformamide, N-dimethylacetamide, dichloroethane, N-methylpyrrolidone, water and ethanol, and 0.2 to 2 milliliters of solvent is corresponding to each 0.1 millimole of cinnamic acid.
As a preferred embodiment of the application according to the invention, wherein: the vinyl sulfone silicon compound can be applied to the fields of catalytic organic synthesis chemistry, pharmaceutical chemistry and material science.
The invention has the beneficial effects that:
(1) The M-Mn-Beta molecular sieve catalyst synthesized by adopting the in-situ doping hydrothermal method has the advantages of easy separation, high activity, good stability, long service life and long storage time. Compared with an ion exchange method and an impregnation method, the M-Mn-Beta molecular sieve synthesized by the in-situ doping hydrothermal method not only prevents Mn particles from gathering and ensures that active Mn species are stably and uniformly dispersed on the Beta molecular sieve with a mesoporous structure, but also has good crystallinity and reduces loss of active metal Mn. The synthesis method has the advantages of convenient operation, simple equipment requirement and good reproducibility.
(2) The M-Mn-Beta molecular sieve catalyst synthesized by the invention contains Lewis acid active sites, can promote the conversion of sodium benzene sulfinate into corresponding benzene sulfinate free radicals, and Mn species can coordinate with carboxyl oxygen atoms in cinnamic acid molecules, thereby remarkably improving the activity of reaction substrates. Meanwhile, the molecular sieve has higher specific surface area and mesoporous structure, so that reactant molecules are easy to contact with active sites, and the diffusion of reactant and product molecules is facilitated. The formed benzene sulfinic acid radical molecule further carries out decarboxylation coupling reaction with cinnamic acid active molecule to remove one molecule of carbon dioxide, thus generating the product (E) - (2- (benzenesulfonyl) vinyl) benzene. The synergistic catalysis obviously improves the catalytic activity of the M-Mn-Beta molecular sieve.
(3) Experiments show that the mesoporous M-Mn-Beta molecular sieve prepared by the invention has higher catalytic decarboxylation coupling reaction performance, and the yield of catalyzing the decarboxylation sulfonylation of cinnamic acid and sodium benzene sulfinate to generate styryl sulfone compound is up to 95%, so that the mesoporous M-Mn-Beta molecular sieve can be applied to the fields of organic synthesis, metal organic chemistry, pharmaceutical chemistry, material science and the like, and has a certain industrial utilization value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a scanning electron microscope image of an M-Mn-Beta molecular sieve catalyst prepared in example 1 of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of an M-Mn-Beta molecular sieve catalyst and standard Beta in example 1 of the present invention;
FIG. 3 is a schematic diagram of N for an M-Mn-Beta molecular sieve catalyst according to example 1 of the present invention 2 Adsorption and desorption curves;
FIG. 4 is a NH of an M-Mn-Beta molecular sieve catalyst of example 1 of the present invention 3 -TPD profile;
FIG. 5 shows the product (E) - (2- (benzenesulfonyl) vinyl) benzene obtained by decarboxylation coupling of cinnamic acid with sodium benzene sulfinate using the M-Mn-Beta molecular sieve prepared in example 1 of the invention 1 H NMR spectrum;
FIG. 6 shows the product (E) - (2- (benzenesulfonyl) vinyl) benzene obtained by decarboxylation coupling of cinnamic acid with sodium benzene sulfinate using the M-Mn-Beta molecular sieve prepared in example 1 of the invention 13 C NMR spectrum;
FIG. 7 is a graph showing the catalytic effect of the M-Mn-Beta molecular sieve catalyst prepared in example 1 of the present invention for six cycles.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The information such as the specifications of the chemical reagents used in the examples of the present invention are shown in Table 1.
TABLE 1 information on specifications of chemical reagents used in experiments
Example 1
The preparation method of the M-Mn-Beta molecular sieve material comprises the following steps:
weighing 5.3g of silicic acid and 0.3g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.5g, the metal content was 1.8wt%, and the specific surface area was 693m 2 And/g, the crystallinity is 100%. Information such as the model of the instrument used in the experiments of the present invention is shown in Table 2.
Table 2 information about model of instrument and equipment used for experiments
The M-Mn-Beta molecular sieve material prepared in example 1 was characterized.
The morphology of M-Mn-Beta is analyzed by a Thermo Scientific Apreo C field emission Scanning Electron Microscope (SEM), and as shown in FIG. 1, the proportional dimensions are 2 μm,1 μm and 200nm respectively, and the results show that the morphology of the M-Mn-Beta molecular sieve is relatively regular and uniform and mainly exists in the form of egg-shaped aggregates with the diameter of 600nm, and each aggregate is assembled by a plurality of primary BEA crystals with the diameter of about 30 nm. The mutual packing of these aggregates creates a number of packing pores that facilitate the dispersion of the metal species and also facilitate the contact of the reactant molecules with the active sites.
The crystal structure and the crystalline phase of the M-Mn-Beta molecular sieve material were analyzed by using a RigakuD/MAX-2500PC type X-ray powder diffractometer (PXRD, cu K alpha radiation, lambda=0.154 nm, scan range 2 theta of 5 DEG-50 DEG, scan speed of 2 DEG/min). The analysis results are shown in fig. 2 and table 3, and the results show that the M-Mn-Beta molecular sieve is completely matched with the crystal phase structure of the Beta molecular sieve, and has a typical BEA structure, thus indicating the successful preparation of the M-Mn-Beta molecular sieve. In addition, no characteristic diffraction peak of the Mn species could be detected in the figure, which indicates that the Mn species of the small particles are highly uniformly dispersed on the Beta molecular sieve. From the point of peak intensity, the M-Mn-Beta has stronger peak intensity and sharp peak shape, which indicates that the M-Mn-Beta molecular sieve material has good crystallinity and provides guarantee for catalyzing the decarboxylation coupling reaction of cinnamic acid.
TABLE 3 Table 3
Adopting Micrometrics ASAP2460 specific surface area and porosity analyzer to measure specific surface area and N of M-Mn-Beta molecular sieve material 2 Adsorption and desorption curves and pore size distribution. Specific surface area is BET squareThe pore size distribution was measured by the BJH method. After drying the sample at 120℃for 2 hours before measurement, it was subjected to a vacuum at 150℃for 12 hours. The measurement results are shown in FIG. 3, N 2 The adsorption and desorption isotherms have a hysteresis at the relative pressure P/p0=0.5-0.99 due to N 2 The capillary condensation phenomenon in the pores of the molecular sieve further shows that the M-Mn-Beta contains a mesoporous structure. From the pore size distribution curve, the pore size of M-Mn-Beta is mainly distributed at 3.7nm and 4.3nm, and the pore size distribution is uniform.
Ammonia gas temperature programmed desorption (NH) on Micrometrics AUTO Chem II 2920 instrument was used 3 TPD) measuring the acidity of the catalyst. The measurement results are shown in FIG. 4, NH 3 The desorption temperature of the catalyst is 123.5 ℃, belongs to the weak acid center range, and further indicates that the M-Mn-Beta molecular sieve has moderate weak acid strength.
Comparative example 1
The ion exchange process of synthesizing M-Mn-Beta molecular sieve catalyst includes the following steps:
(1) Synthesizing the M-Beta molecular sieve by a hydrothermal method:
Weighing 5.3g of silicic acid, dissolving in deionized water, uniformly mixing, adding concentrated hydrochloric acid to adjust the pH to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by using sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol, drying, transferring to a muffle furnace, and roasting for 5 hours at 550 ℃ to obtain the product M-Beta molecular sieve.
(2) The M-Mn-Beta molecular sieve is prepared by an ion exchange method:
weighing 0.3g of manganese chloride tetrahydrate, adding 10 ml of deionized water to dissolve the manganese chloride tetrahydrate, uniformly stirring the manganese chloride tetrahydrate, adding the prepared M-Beta molecular sieve, stirring the manganese chloride tetrahydrate, performing ion exchange at room temperature, drying the manganese chloride tetrahydrate at 100 ℃ overnight, tabletting and sieving the manganese chloride tetrahydrate to obtain the M-Mn-Beta molecular sieve.
The product mass was 1.7g, the metal content was 1.5wt% and the specific surface area was 616m 2 And/g, the crystallinity is 80%.
Comparative example 2
The method for preparing the M-Mn-Beta by the isovolumetric impregnation method comprises the following steps:
firstly, the water absorption rate of the Beta molecular sieve carrier is measured, and the catalyst is impregnated in an equal volume according to the water absorption rate. 0.3g of manganese chloride tetrahydrate was weighed out and dissolved with deionized water. Adding 1gM of molecular sieve carrier (silicon-aluminum ratio 40, crystallinity 100%), stirring thoroughly, mixing homogeneously by ultrasound, ageing for 5 hours at room temperature, drying at 80 deg.C, roasting for 5 hours at 550 deg.C in muffle furnace, and obtaining M-Mn-Beta molecular sieve.
The product mass was 1.9g, the metal content was 1.7wt%, and the specific surface area was 658m 2 /g, crystallinity 85%.
As can be seen from examples 1 and comparative examples 1 and 2, the in-situ doping synthesis method has the advantages of more convenient operation, high catalyst yield, high crystallinity and the like compared with the ion exchange method and the impregnation method. In addition, the interaction between Mn species in the M-Mn-Beta catalyst synthesized by in-situ doping hydrothermal and the M-Beta molecular sieve is stronger, so that Mn is highly dispersed on the molecular sieve, and therefore, the catalyst has higher catalytic activity. The following examples screen the raw materials or the mixture ratio of the in situ doping method for synthesizing M-Mn-Beta.
Example 2
Weighing 5.3g of silicic acid and 0.2g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.3g, the metal content was measured to be 1.3wt%, and the specific surface area was measured to be 671m 2 And/g, the crystallinity is 98%.
Example 3
Weighing 5.3g of silicic acid and 0.3g of manganese nitrate tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH value of the solution to 1.0, then adding 13.7g of tetraethylammonium bromide and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH value of the solution to 12.5 by using sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.1g, the metal content was 1.4wt%, and the specific surface area was 593m 2 Per g, the crystallinity is 83%.
Example 4
Weighing 5.3g of silicic acid and 0.5g of manganese acetate dihydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of tetrapropylammonium hydroxide and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by using sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
Washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.6g, the metal content was measured to be 2.3wt%, and the specific surface area was measured to be 622m 2 Per g, the crystallinity is 87%.
Example 5
Weighing 5.3g of silicic acid and 0.3g of manganese sulfate tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of cetyl trimethyl ammonium bromide and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by using sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.2g, the metal content was 1.5wt% and the specific surface area was 677m 2 And/g, the crystallinity is 98%.
Example 6
Weighing 5.3g of silicic acid and 0.5g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 6.8g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
Transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.6g, the metal content was measured to be 2.2wt%, and the specific surface area was measured to be 532m 2 And/g, crystallinity of 91%.
Example 7
Weighing 5.3g of silicic acid and 0.3g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 9.8g of 25% tetraethylammonium hydroxide aqueous solution and 0.8g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at the constant temperature of 140 ℃ for 14 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.1g, the metal content was 1.6wt% and the specific surface area was measured to be 525m 2 And/g, the crystallinity is 88%.
Example 8
Weighing 5.3g of silicic acid and 0.3g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.26g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
Transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing for 15 days at a constant temperature of 100 ℃;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was 1.8g, the metal content was 1.1wt%, and the specific surface area was 588m 2 And/g, crystallinity of 93%.
Example 9
Weighing 5.3g of silicic acid and 0.3g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing at a constant temperature of 150 ℃ for 7 days;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was measured to be 2.1g, the metal content was 1.5wt%, and the specific surface area was 615m 2 Per g, the crystallinity is 96%.
Example 10
Weighing 5.3g of silicic acid and 0.3g of manganese chloride tetrahydrate, dissolving in deionized water, uniformly mixing, dropwise adding concentrated hydrochloric acid to adjust the pH of the solution to 1.0, then adding 13.7g of 25% tetraethylammonium hydroxide aqueous solution and 0.4g of sodium metaaluminate, uniformly stirring, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
Transferring the mixed solution into a 50 ml polytetrafluoroethylene high-pressure hydrothermal kettle, and crystallizing for 5 days at the constant temperature of 200 ℃;
washing with deionized water and absolute ethyl alcohol to be neutral, drying, transferring to a muffle furnace, and roasting at 550 ℃ for 5 hours to obtain the product M-Mn-Beta molecular sieve.
The product mass was 1.5g, the metal content was 0.9wt%, the specific surface area473m 2 Per g, the crystallinity is 87%.
Example 11
The decarboxylation coupling reaction performance of the M-Mn-Beta molecular sieve material in example 1 for catalyzing cinnamic acid was studied.
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
After the reaction is finished, the catalyst is subjected to centrifugal separation, the reaction liquid is subjected to detection analysis by SHIMADZU high performance liquid chromatography, and the product is separated by column chromatography.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene with a yield of 95.1%.
The product is 1 The H NMR spectrum is shown in figure 5, 13 the C NMR spectrum is shown in FIG. 6.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.02–7.88(m,2H),7.69(d,J＝15.4Hz,1H),7.64–7.51(m,3H),7.50–7.34(m,5H),6.87(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ142.5,140.7,133.4,132.4,131.3,129.4,129.1,128.6,127.7,127.3.
test conditions:
adopts SHIMADZU LC-VP high performance liquid chromatograph, and the mobile phase is acetonitrile and water gradient elution (V Acetonitrile :V Water and its preparation method =6:4), the detection wavelength of the ultraviolet detector was 274nm, and the flow rate was 1.0mL/min.
Adopts a German Bruker company AVANCE III M type nuclear magnetic resonance apparatus with the working frequency of 300MHz 1 H) The method comprises the steps of carrying out a first treatment on the surface of the Super shielding magnet with magnetic field strength 9.4T; a positive broadband liquid probe is configured. The chemical shift of protons is recorded in ppm and is based on deuterated residues in TMS or NMR solvents (deuterated chloroform, δ7.26). Chemical shifts of carbon are reported in ppm and are based on carbon resonance of the reference solvent (deuterated chloroform, delta 77.16). The data represent the coupling constant in hertz (Hz), the integral.
Example 12
0.5mmol of cinnamic acid, 0.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 79.3%.
Example 13
0.5mmol of cinnamic acid, 2.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta,1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 90.5%.
Example 14
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 0.1mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product is proved to be (E) - (2- (phenylsulfonyl) vinyl) benzene by NMR and high performance liquid chromatography, and the yield is only 6.3 percent, because the use amount of the M-Mn-Beta catalyst is too low, which greatly reduces the reaction efficiency.
Example 15
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 5.0mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 91.6%.
Example 16
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 0.5mmol of potassium iodide and 1 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product is proved to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography, and the yield is 8.5%, which shows that the yield of the reaction can be obviously reduced when the use amount of the additive potassium iodide and the solvent dimethyl sulfoxide is reduced at the same time, and further shows that the potassium iodide and the dimethyl sulfoxide are critical to the reaction.
Example 17
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 2.5mmol of potassium iodide and 10 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 87.2%.
Example 18
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of sodium iodide and 4 ml of N, N-dimethylformamide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene with a yield of 70.3%.
Example 19
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of ammonium iodide and 4 ml of N, N-dimethylacetamide were introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 61.5%.
Example 20
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of elemental iodine and 4 ml of dichloroethane are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography with a yield of only 0.5%, indicating that the reaction proceeded to a very low extent when the additive was changed to elemental iodine and the solvent was changed to dichloroethane.
Example 21
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium carbonate and 4 ml of N-methylpyrrolidone are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product is proved to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography, the yield is only 0.3%, and the product is proved to be unsuitable for the reaction system by taking potassium carbonate as an additive and N-methylpyrrolidone as a solvent.
Example 22
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium chloride and 4 ml of water were introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography with a yield of 16.5%, indicating that neither potassium chloride as an additive nor water as a solvent was the optimal choice for the reaction.
Example 23
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium bromide and 4 ml of ethanol are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography with a yield of 13.2%, indicating that neither potassium bromide as an additive nor ethanol as a solvent was the optimal choice for the reaction.
Example 24
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 50℃for 1 hour.
The structure of the product was confirmed to be (E) - (2- (benzenesulfonyl) vinyl) benzene by NMR and high performance liquid chromatography, and the yield was 2.8%, indicating that the simultaneous reduction of the reaction temperature and reaction time significantly reduced the efficiency of the reaction.
Example 25
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 70℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 65.9%.
Example 26
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 100℃for 24 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene with a yield of 89.7%.
Example 27
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 150℃for 20 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene with a yield of 93.1%.
Example 28
0.5mmol of 2-methyl cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-methyl-2- (2- (phenylsulfonyl) vinyl) benzene in a yield of 78.2%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.05–7.87(m,3H),7.66–7.51(m,3H),7.43(d,J＝7.8Hz,1H),7.33–7.14(m,3H),6.79(d,J＝15.3Hz,1H),2.45(s,3H). 13 C NMR(75MHz,CDCl 3 )δ140.7,140.1,138.2,133.4,131.4–130.9,129.4,128.1,127.7,126.9,126.5,19.8.
example 29
0.5mmol of 3-methylcinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-methyl-3- (2- (benzenesulfonyl) vinyl) benzene in a yield of 82.3%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.95(dt,J＝3.6,2.5Hz,2H),7.71–7.46(m,4H),7.33–7.16(m,4H),6.85(d,J＝15.4Hz,1H),2.34(s,3H). 13 C NMR(75MHz,CDCl 3 )δ142.7,140.8,138.9,133.4,132.2,129.5–128.9,127.7,127.0,125.9,21.3.
example 30
0.5mmol of 2-ethoxycinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-ethoxy-2- (2- (benzenesulfonyl) vinyl) benzene in 75.1% yield.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.93(ddd,J＝24.2,12.7,8.3Hz,1H),7.68–7.47(m,1H),7.43–7.27(m,1H),7.09(d,J＝15.5Hz,1H),6.91(dd,J＝15.5,8.0Hz,1H),4.08(q,J＝7.0Hz,1H),1.43(t,J＝7.0Hz,1H). 13 CNMR(75MHz,CDCl 3 )δ158.2,141.2,138.7,133.1,132.5,130.9,129.3,127.7,127.5,121.1,120.6,112.1,64.1,14.7.
example 31
0.5mmol of 4-methoxycinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-methoxy-4- (2- (phenylsulfonyl) vinyl) benzene in a yield of 79.4%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.98–7.90(m,2H),7.67–7.39(m,6H),6.95–6.84(m,2H),6.73(t,J＝11.9Hz,1H),3.80(d,J＝14.2Hz,3H). 13 C NMR(75MHz,CDCl 3 )δ162.1,142.4,141.2,133.3,130.5,129.3,127.6,125.0,124.4,114.6,55.5.
example 32
0.5mmol of 3-fluorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide were added to a 15 ml three-necked flask equipped with a magnetic stirring bar, and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-fluoro-3- (2- (benzenesulfonyl) vinyl) benzene in a yield of 72.1%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.03–7.88(m,2H),7.71–7.50(m,4H),7.44–7.33(m,1H),7.31–7.24(m,1H),7.22–7.06(m,2H),6.89(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ164.6,161.3,141.0,141.0,140.3,134.6,134.5,133.6,130.8,130.7,129.5,128.8,127.8,124.7,124.7,118.3,118.0,115.0,114.7.
example 33
0.5mmol of 4-fluorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide were added to a 15 ml three-necked flask equipped with a magnetic stirring bar, and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-fluoro-4- (2- (benzenesulfonyl) vinyl) benzene in a yield of 76.3%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.02–7.88(m,2H),7.69(d,J＝15.4Hz,1H),7.64–7.51(m,3H),7.50–7.34(m,5H),6.87(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ166.1,162.7,141.2,140.6,133.5,130.8,130.6,129.5,128.7,128.6,127.7,127.1,127.0,116.6,116.3.
example 34
0.5mmol of 2, 4-difluorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -2, 4-difluoro-1- (2- (benzenesulfonyl) vinyl) benzene in 46.8% yield.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.00–7.89(m,2H),7.75–7.40(m,5H),7.00–6.81(m,3H). 13 C NMR(75MHz,CDCl 3 )δ140.4,134.5,133.6,131.6,130.0–129.4,127.8,112.5,105.4,105.0,104.7.
example 35
0.5mmol of 2-chlorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-chloro-2- (2- (benzenesulfonyl) vinyl) benzene in a yield of 70.2%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.98–7.92(m,2H),7.76(d,J＝15.6Hz,1H),7.66–7.51(m,3H),7.49–7.34(m,2H),7.20–6.98(m,3H). 13 C NMR(75MHz,CDCl 3 )δ163.3,159.9,140.5,135.6,135.6,133.6,132.9,132.8,130.4,130.4,130.3,130.2,129.4,127.8,124.8,124.7,120.7,120.5,116.3.
example 36
0.5mmol of 3-chlorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-chloro-3- (2- (benzenesulfonyl) vinyl) benzene in 66.7% yield.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.99–7.88(m,2H),7.69–7.51(m,4H),7.46(d,J＝1.8Hz,1H),7.41–7.24(m,3H),6.88(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ140.8,140.4,135.2,134.2,133.7,131.1,130.4,129.5,129.0,128.3,127.8,126.9.
example 37
0.5mmol of 4-chlorocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-chloro-4- (2- (benzenesulfonyl) vinyl) benzene in a yield of 72.3%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.99–7.89(m,2H),7.67–7.50(m,4H),7.45–7.31(m,4H),6.85(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ141.0,140.5,137.3,133.6,130.9,129.8,129.5,128.0,127.7.
example 38
0.5mmol of 3-bromocinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-bromo-3- (2- (phenylsulfonyl) vinyl) benzene in a yield of 62.6%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.97(dt,J＝3.6,2.4Hz,2H),7.71–7.50(m,6H),7.41(t,J＝7.9Hz,1H),7.29(dd,J＝8.8,6.9Hz,1H),6.90(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ140.7,140.3,134.4,134.0,133.7,131.1,130.6,129.5,128.9,127.8,127.3,123.2.
example 39
0.5mmol of cinnamic acid, 1.5mmol of sodium 4-methylbenzenesulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-methyl-4- (styrenesulfonyl) benzene in a yield of 91.5%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.86–7.79(m,2H),7.64(t,J＝10.3Hz,1H),7.50–7.43(m,2H),7.42–7.29(m,5H),6.84(t,J＝9.8Hz,1H),2.44–2.39(m,3H). 13 C NMR(75MHz,CDCl 3 )δ144.4,141.9,137.7,132.4,131.1,130.0,129.1,128.5,127.7,21.6.
example 40
0.5mmol of cinnamic acid, 1.5mmol of sodium 4-fluorobenzenesulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide were added to a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-fluoro-4- (styrenesulfonyl) benzene in 88.2% yield.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ8.02–7.89(m,2H),7.68(d,J＝15.4Hz,1H),7.53–7.34(m,5H),7.28–7.16(m,2H),6.90–6.78(m,1H). 13 C NMR(75MHz,CDCl 3 )δ167.4,164.0,142.7,136.8,132.3,131.4,130.6,129.2,128.7,127.1,116.9,116.6.
example 41
0.5mmol of cinnamic acid, 1.5mmol of sodium 4-chlorobenzenesulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide were introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) -1-chloro-4- (styrenesulfonyl) benzene in a yield of 82.1%.
The NMR results of the product were analyzed as: 1 H NMR(300MHz,CDCl 3 )δ7.93–7.83(m,2H),7.68(d,J＝15.4Hz,1H),7.55–7.44(m,4H),7.43–7.33(m,3H),6.85(d,J＝15.4Hz,1H). 13 C NMR(75MHz,CDCl 3 )δ143.1,140.1,139.3,132.2,131.5,129.7,129.2,128.7,126.8.
example 42
M-Mn-Beta cycle use test:
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared in example 1), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are introduced into a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
After the reaction is finished, the catalyst is centrifugally separated, washed by deionized water and absolute ethyl alcohol for a plurality of times, then placed in a drying oven and dried for 12 hours at 100 ℃, the catalytic effect of the dried catalyst after being recycled for six times under the same catalytic condition is shown in figure 7, and the result shows that the catalytic activity is basically unchanged after being recycled for six times.
Comparative example 3
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of manganese chloride tetrahydrate, 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are added to a 15 ml three-necked flask equipped with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 23.5%.
Comparative example 4
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of nano manganese chloride, 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are added to a 15 ml three-necked flask with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in 15.7% yield.
Comparative example 5
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of beta molecular sieve, 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are added to a 15 ml three-necked flask with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 0.2%.
Comparative example 6
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared by ion exchange method), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are added to a 15 ml three-necked flask with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 51.6%.
Comparative example 7
0.5mmol of cinnamic acid, 1.5mmol of sodium benzene sulfinate, 1.5mmol of M-Mn-Beta (prepared by an isovolumetric infusion method), 1.5mmol of potassium iodide and 4 ml of dimethyl sulfoxide are added to a 15 ml three-necked flask with a magnetic stirring bar and reacted at 130℃for 9 hours.
The structure of the product was confirmed by NMR and high performance liquid chromatography to be (E) - (2- (phenylsulfonyl) vinyl) benzene in a yield of 63.8%.
The invention discloses a method for synthesizing an acidic Beta zeolite molecular sieve catalyst containing a mesoporous structure by metal manganese in-situ doping hydrothermal method and application of the catalyst in catalyzing cinnamic acid decarboxylation coupling reaction to generate a vinyl sulfone compound, and relates to the field of heterogeneous catalysts for constructing the vinyl sulfone compound by decarboxylation coupling reaction. The preparation method of the in-situ doped hydrothermal method comprises the following steps: taking silicic acid, sodium metaaluminate and manganese salt as raw materials, crystallizing for 14 days at the constant temperature of 140 ℃ in the presence of a quaternary ammonium salt template agent to obtain the M-Mn-Beta molecular sieve catalyst with the specific surface area of 435-693M 2 And/g, wherein the silicon-aluminum ratio is 20:1-60:1, and the crystallinity is 85-100%. The prepared catalyst has the advantages of economy, high efficiency, environmental protection and the like, and can improve the defects of difficult recovery and recycling of the homogeneous catalyst.
The preparation method of the invention has convenient operation and good reproducibility. The acidic M-Mn-Beta molecular sieve containing the mesoporous structure is used for catalyzing decarboxylation coupling reaction of cinnamic acid and sodium benzene sulfinate, the yield of the prepared (E) - (2- (benzenesulfonyl) vinyl) benzene can reach 95 percent, and the catalyst still has higher catalytic activity and no metal loss after being recycled for a plurality of times. Therefore, the method can be applied to the fields of modern organic catalytic synthesis of organic vinyl sulfone compounds and the like, and has a certain industrial application prospect.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.

Claims (10)

1. A manganese doped acidic Beta zeolite molecular sieve containing a mesoporous structure is characterized in that: the molecular sieve has a structure of Mn-nSi-Al-Beta, wherein n represents the molar ratio of Si/Al, and n=20-60;
the acidic Beta zeolite molecular sieve has a characteristic X-ray powder diffraction pattern as shown below:
Wherein the X-ray powder diffraction pattern is based on a relative intensity scale, wherein the strongest line in the X-ray powder diffraction pattern is designated as the value 100, when the corresponding relative intensity is: w represents weak, i.e. 20 or less; m represents, i.e. > 20 to ∈40; s represents strong, i.e. > 40 to 60; and vs represents very strong, i.e. > 60.
2. The acidic Beta zeolite molecular sieve of claim 1, wherein: the specific surface area of the acidic Beta zeolite molecular sieve is 435-693 m 2 And/g, wherein the silicon-aluminum ratio is 20:1-60:1, and the crystallinity is 85-100%.
3. A process for preparing an acidic zeolite Beta molecular sieve according to claim 1 or 2, characterized in that: comprising the steps of (a) a step of,
mixing silicic acid, manganese salt and deionized water uniformly, dropwise adding concentrated hydrochloric acid to adjust the pH to 1.0, then adding quaternary ammonium salt and sodium metaaluminate, stirring uniformly, and then adjusting the pH of the solution to 12.5 by sodium hydroxide;
transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and crystallizing for a period of time at a constant temperature;
washing with deionized water and absolute ethyl alcohol, drying, and roasting at 550 ℃ for 5 hours to obtain the manganese doped acidic Beta molecular sieve catalyst M-Mn-Beta containing mesoporous structure.
4. A method of preparation as claimed in claim 3, wherein: the mass ratio of the silicic acid to the sodium metaaluminate is 20:1-60:1.
5. A method of preparation as claimed in claim 3, wherein: the quaternary ammonium salt is one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and hexadecyl trimethyl ammonium bromide, and each 1g of silicic acid corresponds to 1.2-3 g of quaternary ammonium salt; the manganese salt is one or a mixture of a plurality of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride, and each 1g of silicic acid corresponds to 0.03-0.1 g of manganese salt.
6. A method of preparation as claimed in claim 3, wherein: and crystallizing for a period of time at a constant temperature, wherein the crystallization temperature is 100-200 ℃ and the crystallization time is 5-15 days.
7. Use of the acidic zeolite Beta molecular sieve prepared by the preparation method according to any one of claims 3 to 6, characterized in that: the acidic Beta zeolite molecular sieve is applied to catalyzing the decarboxylation and sulfonylation reaction of cinnamic acid and sodium benzene sulfinate to prepare a vinyl sulfone compound, wherein the preparation method comprises the steps of mixing cinnamic acid, sodium benzene sulfinate, an acidic Beta zeolite catalyst M-Mn-Beta, an additive and a solvent, and reacting for 1-24 hours at 50-150 ℃ to obtain the vinyl sulfone silicon compound.
8. The use according to claim 7, wherein: the cinnamic acid is at least one of cinnamic acid and derivatives thereof, 2-methyl cinnamic acid, 3-methyl cinnamic acid, 2-ethoxy cinnamic acid, 4-methoxy cinnamic acid, 3-fluoro cinnamic acid, 4-fluoro cinnamic acid, 2, 4-difluoro cinnamic acid, 2-chloro cinnamic acid, 3-chloro cinnamic acid, 4-chloro cinnamic acid and 3-bromo cinnamic acid; the sodium benzene sulfinate is at least one of sodium benzene sulfinate and its derivatives, sodium 4-methyl benzene sulfinate, sodium 4-fluorobenzene sulfinate and sodium 4-chlorobenzene sulfinate; the mass ratio of cinnamic acid to sodium benzene sulfinate is 1:1-1:5; the addition amount of the acidic Beta molecular sieve catalyst M-Mn-Beta is 0.1 to 5mol percent of the amount of cinnamic acid substances.
9. The use according to claim 7, wherein: the additive is KI, naI, NH 4 I、I 2 、K 2 CO 3 0.1-0.5 millimole of additive corresponding to 0.1 millimole of cinnamic acid in one of KCl and KBr; the solvent is one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, dichloroethane, N-methylpyrrolidone, water and ethanol, and each 0.1 millimole of cinnamic acid corresponds to 0.2-2 milliliters of solvent.
10. The use according to claim 7, wherein: the vinyl sulfone silicon compound can be applied to the fields of catalytic organic synthesis chemistry, pharmaceutical chemistry and material science.
CN202311372178.4A 2023-10-23 2023-10-23 Preparation method and application of manganese doped mesoporous structure-containing acidic Beta zeolite molecular sieve Pending CN117430125A (en)

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