CN116532109A - Preparation method of supported catalyst, obtained product and application - Google Patents

Preparation method of supported catalyst, obtained product and application Download PDF

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Publication number
CN116532109A
CN116532109A CN202310483060.2A CN202310483060A CN116532109A CN 116532109 A CN116532109 A CN 116532109A CN 202310483060 A CN202310483060 A CN 202310483060A CN 116532109 A CN116532109 A CN 116532109A
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catalyst
reaction
preparation
diethanolamine
oxazolidine
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刘晓磊
孙国新
蒋绪川
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University of Jinan
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University of Jinan
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7003—A-type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a preparation method of a supported catalyst, a product obtained by the preparation method and application of the supported catalyst, wherein porous materials, aluminum trichloride, a silane coupling agent and a solvent are mixed for reaction; and (3) filtering and drying after the reaction, and calcining the obtained catalyst precursor to obtain the supported catalyst. The catalyst has the advantages of simple preparation method, wide application in catalyzing and preparing the polyurethane system hydroxy oxazolidine, high reaction rate of the hydroxy oxazolidine after the catalyst is used, cyclic utilization of the catalyst, easy separation of products, high purity of the products, no color, clarity and good storage stability. Meanwhile, the catalyst can also effectively catalyze the synthesis of Fischer indole, and the catalytic yield is not obviously reduced after multiple cycles.

Description

Preparation method of supported catalyst, obtained product and application
Technical Field
The invention relates to a preparation method of a supported catalyst and an obtained product, and also relates to application of the supported catalyst in preparation of polyurethane system hydroxyl oxazolidine and synthesis of Fischer indole, belonging to the technical field of catalysts.
Background
The oxazolidine compound has wide application in polyurethane elastomer materials, polyurethane coatings and waterproof materials, can be used as a water removing agent in a polyurethane reaction system, a reactive diluent of high-solid-content coatings, a latent curing agent of single-component moisture-curing coatings and sealants and a storage stabilizer, and can be used for preparing coating components. In a polyurethane system, the oxazolidine and water or moisture react preferentially to generate active groups, and then the active groups and isocyanate groups are rapidly crosslinked and cured to form a film, so that the effects of moisture removal and effective curing are achieved, and based on the characteristics, the structure of the hydroxyl oxazolidine is gradually paid attention to and developed. At present, with the intensive research on an oxazolidine skeleton and branching action thereof, technological research on oxazolidine compounds is gradually paid attention to, but at present, the industrial problems of low yield and difficult industrialization still exist.
CN 105111158A reacts with isobutyraldehyde to prepare the hydroxyl oxazolidine in a mode of large excess of diethanolamine, the chroma of the product is deep, meanwhile, separation of the product can be realized only by distillation, and the defect that the raw diethanolamine with excessive high-boiling byproducts is difficult to separate is caused, and the reported mode of CN202011641642.1 is similar. The synthetic methods described in the literature "university of western safety national (natural science edition), 2006, 32 (3), 529-532" have low yields and also suffer from high product chromaticity. JP 200888220, JP2009119358, JP2008222792, JP2009067917, JP2016145321 and the like adopt toluene as a water-carrying agent to promote the reaction of diethanolamine and isobutyraldehyde to the right, but the reaction temperature is higher, the yield is lower, and meanwhile, the chromaticity problem of the product is difficult to solve, and toluene is easy to remain in the product, so that the product has strong toluene smell. The method reported in the literature "Izvestiya Natsional' noi Akademii Nauk Respubliki Kazakhstan, seriya Khimicheskaya,2007, (2), 40-44" uses microwaves as a heat source to promote the reaction of diethanolamine and isobutyraldehyde, but the separation of water cannot be achieved in the process, resulting in serious hydrolysis of the product. In the method reported in the literature "Eur.Pat.Appl.,414962", benzene is used as a solvent, and diisopropanolamine reacts with isobutyraldehyde, so that the defects of high product chromaticity and low reaction yield are overcome.
From the prior art, the synthesis of the hydroxyl oxazolidine is generally constructed by adopting a diethanolamine structure and aldehyde condensation, water generated in the reaction process inhibits the reaction, and all reports in the prior art are based on the promotion of the reaction by carrying water with a water carrying agent, but the method still has the defects of low yield and high product chromaticity, and cannot realize large-scale production. Meanwhile, no report is found that dehydration between alcohol amine and aldehyde molecules and intramolecular condensation are promoted by adding a catalyst, so that efficient production of the product is realized.
Through analysis of the reaction mechanism, the reaction site of the catalyst should promote imine formation and promote transfer of intramolecular bonds, so that hydroxyl is attacked to form an oxazole ring, and the target product is formed after deprotonation. The mechanism shows that the catalyst for promoting the product generation is different from the traditional acid or Lewis acid catalyst, and the traditional catalyst can combine with hydroxyl to form a catalyst with good leaving propertyThe salt forms a carbocation after leaving, and is different from a structure formed by the reaction, and the carbocation is also the reason that no catalyst participates in the reaction. Therefore, by analyzing the action mechanism of the structure in a polyurethane system and researching the structure-activity relationship of the compound, a catalyst for promoting the formation of imine and promoting the transfer of intramolecular bonds is found to have important significance for the process synthesis of the hydroxyl oxazolidine.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of a supported catalyst and the obtained supported catalyst. The catalyst has the advantages of simple preparation method, wide application in catalyzing and preparing polyurethane system hydroxy oxazolidine, fast hydroxy oxazolidine reaction rate, cyclic utilization of the catalyst, easy separation of products, high purity of products, no color, clarity and good storage stability. Meanwhile, the catalyst can also effectively catalyze the synthesis of Fischer indole, and the catalytic yield is not obviously reduced after multiple cycles.
The invention is realized by the following technical scheme:
a method for preparing a supported catalyst, the method comprising the steps of:
(1) Mixing porous material, aluminum trichloride, silane coupling agent and solvent for reaction;
(2) And (3) filtering and drying after the reaction, and calcining the obtained catalyst precursor to obtain the supported catalyst.
Further, in the step (1), the following raw materials are used in parts by weight: 50-70 parts of porous material, 0.1-2.0 parts of aluminum trichloride and 1-10 parts of silane coupling agent.
Further, in the step (1), the porous material is used in an amount of 50 parts by weight, 60 parts by weight or 70 parts by weight.
Further, in the step (1), aluminum trichloride is used in an amount of 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.8 part by weight, 1.0 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight or 2.0 parts by weight.
Further, in the step (1), the silane coupling agent is used in an amount of 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
Further, in the step (1), the amount of the solvent may be selected according to the actual situation, and in a specific embodiment of the present invention, the amount of the solvent is 100-200 parts by weight, for example, 100 parts by weight, 120 parts by weight, 150 parts by weight, 175 parts by weight, 200 parts by weight.
Further, in the step (1), the silane coupling agent is a silane coupling agent KH570, a silane coupling agent KH580 or a silane coupling agent NXT.
Further, in the step (1), the porous material is a porous inorganic compound, preferably a vesuvianite or a molecular sieve, and the molecular sieve is a type 3A, type 4A or type 5A molecular sieve, more preferably a type 4A molecular sieve. The volcanic rock and the molecular sieve are non-acidic porous materials with few active catalytic sites, and the invention selects the silane coupling agent and the aluminum trichloride as the modifier to modify or regulate the acidic sites of the volcanic rock and the molecular sieve, so that the introduction of the silicon element and the aluminum element has a synergistic effect, and the catalytic performance of the whole catalyst is improved.
Further, in the step (1), the solvent is an alcohol solvent, preferably one or more of methanol, ethanol, isopropanol, and n-butanol, and more preferably ethanol.
Further, in the step (1), the porous material and the solvent are mixed, and then the temperature is controlled, and aluminum trichloride and the silane coupling agent are added under stirring to carry out a modification reaction. The reaction temperature is 10-80deg.C, such as 10deg.C, 15deg.C, 20deg.C, 25deg.C, 30deg.C, 40deg.C, 50deg.C, 60deg.C, 70deg.C, 80deg.C. The reaction time is generally 20 to 200 minutes, for example 20 minutes, 50 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes.
Further, in the step (2), the calcination temperature is 700 to 880 ℃, for example, 700 ℃, 720 ℃, 740 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃. Calcination times are generally from 2 to 8 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours.
The invention realizes the preliminary modification of the porous inorganic material by the surface modification of the porous material by the silane coupling agent and the modification of the pore canal by the aluminum trichloride, forms the silica site by calcination, realizes the adjustment of the surface active site and the acid site of the porous inorganic material, and finally realizes the efficient catalysis of the reactions such as the hydroxyl oxazolidine and the like by multi-effect synergy. The catalyst prepared by the method disclosed by the invention has a stable structure and can be recycled, and the catalyst has outstanding advantages in the field of preparing the polyurethane system hydroxyl oxazolidine by catalysis and the field of preparing indole compounds by Fischer indole synthesis reaction, so that the catalyst and the application of the catalyst in preparing the polyurethane system hydroxyl oxazolidine and indole compounds are also in the protection scope of the invention.
Specifically, the invention also provides a preparation method of the hydroxyl oxazolidine, which takes diethanolamine and derivatives thereof as substrates and takes the supported catalyst as a catalyst to react under the protection of gas to obtain the hydroxyl oxazolidine. The reaction formula is as follows:
the hydroxy oxazolidine has a structural formula shown in the following formula (1):
in the formula (1), R is one of hydrogen and methyl, and R' is one of isopropyl and n-propyl.
Preferably, R is hydrogen and R' is isopropyl.
Further, in the above preparation method, the diethanolamine and the derivative thereof are diethanolamine or diisopropanolamine; the aldehyde is isobutyraldehyde or n-butyraldehyde.
Further, in the above preparation method, the molar ratio of diethanolamine and its derivatives to aldehyde is 1:1 to 3, preferably 1:2.5.
Further, in the preparation method, 0.1g to 0.25g of catalyst is added to 1mol of diethanolamine and the derivative thereof.
Further, in the above preparation method, the reaction is performed under a gas atmosphere to prevent oxidation of the raw materials. The shielding gas is inert gases such as nitrogen, argon and the like.
Further, in the above preparation method, the reaction is carried out in an organic solvent, and the solvent disclosed in the prior art, such as cyclohexane, hexane, toluene, etc., may be used. The amount of the solvent may be selected according to the actual situation.
Further, in the above preparation method, the reaction is carried out under reflux for a period of usually 2 to 8 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours. The water produced is continuously separated out during the reaction.
Further, in the preparation method, the reaction comprises the following specific steps: adding diethanolamine and derivatives thereof, aldehyde, an organic solvent and a catalyst into a reaction kettle, raising the temperature to reflux temperature under the protection of inert gas to perform reaction, removing water in the reaction process by a water remover or a reflux condenser and a reflux receiving tank arranged in a reflux system, ending the reaction after the theoretical water removal amount is reached, and obtaining a final product through aftertreatment. The post-treatment can be performed in any one of the following modes, wherein the mode one is as follows: and (3) recycling the organic solvent and the low-boiling point raw materials from the reaction liquid, and distilling under reduced pressure to obtain a product, wherein residues in the reaction kettle are high-boiling point byproducts and catalysts. The mixture of high-boiling point byproducts and the catalyst can be subjected to solid-liquid separation in an ethyl acetate washing mode, and the catalyst is recovered and recycled. The second mode is as follows: filtering the reaction liquid, removing the catalyst, recovering the solvent and the low-boiling raw material from the filtrate, and finally obtaining the target product through reduced pressure distillation.
Furthermore, the invention also provides a preparation method of the indole compound, which takes phenylhydrazine and derivatives thereof and aldehyde as raw materials, takes the supported catalyst as the catalyst and obtains the indole compound through the Fischer indole synthesis reaction.
Furthermore, in the preparation method of the indole compound, the phenylhydrazine and the derivative thereof are phenylhydrazine, p-chlorophenylhydrazine or p-bromophenylhydrazine. The aldehyde is n-butyraldehyde or isovaleraldehyde.
Furthermore, in the preparation method of the indole compound, the molar ratio of phenylhydrazine and derivatives thereof to aldehyde is 1:1.1-1.2.
Further, in the preparation method of indole compounds, the reaction is carried out under the protection of gas so as to prevent the oxidation of raw materials. The shielding gas is inert gases such as nitrogen, argon and the like.
Further, in the above-mentioned process for producing indole compounds, the reaction is carried out in an organic solvent, which may be selected according to reports of the prior art, for example, toluene or the like.
Furthermore, in the preparation method of the indole compound, 2-4mg of catalyst is added per 1mmol of phenylhydrazine and derivatives thereof.
Furthermore, in the preparation method of the indole compound, the reaction temperature is 100-120 ℃.
The invention has the following beneficial effects:
1. the invention takes porous inorganic compounds such as vesuvianite, molecular sieve and the like as basic materials, adopts aluminum trichloride and silane coupling agent to modify the basic materials, and obtains the supported catalyst after calcination.
2. The catalyst provided by the invention can promote intermolecular dehydration of alcohol amine and aldehyde, has the advantages of high reaction rate, low energy consumption, high yield, easiness in separation of a final product, high purity, no color, clarification, good storage stability (after being placed for 180 days in a sealed manner, no change in nuclear magnetic hydrogen spectrum) and high yield, and solves the problems of difficult product separation, low purity, high chromaticity, low yield and the like in the conventional preparation method of the hydroxyl oxazolidine.
3. The catalyst can also effectively catalyze the synthesis of Fischer indole, has high reusability, can be used for a long time after being recycled, and has no obvious reduction of catalytic yield after 15 times of circulation.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine product.
FIG. 2 is a nuclear magnetic carbon spectrum of a 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine product.
FIG. 3 is a nuclear magnetic resonance spectrum of a 2-isopropyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine product.
FIG. 4 is a nuclear magnetic carbon spectrum of a 2-isopropyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine product.
FIG. 5 is a nuclear magnetic resonance spectrum of a 2-propyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine product.
FIG. 6 is a nuclear magnetic resonance spectrum of a 2-propyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine product.
Detailed Description
The following specific examples are presented to illustrate the present invention, and those skilled in the art will readily appreciate the additional advantages and capabilities of the present invention as disclosed herein. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. It is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and to which this invention belongs, and any method, apparatus, or material of the prior art similar or equivalent to the methods, apparatus, or materials described in the examples of this invention may be used to practice the invention.
The vacuum distillation of the invention in application examples 1-10 and application examples 12-14 adopts a laboratory common water circulation pump, and the application example 11 adopts a jet pump, and the vacuum degree is 6-8 KPa.
Unless otherwise indicated, the parts in the examples below are parts by weight.
Catalyst preparation method
Example 1
50 parts of vesuvianite, 150 parts of absolute ethyl alcohol and 0.1 part of aluminum trichloride and 580 parts of silane coupling agent KH are added into an open container, stirring is carried out at room temperature, stirring is stopped after 2 hours, suction filtration is carried out, drying treatment is carried out at 110 ℃ for 2 hours in a drying oven to obtain a catalyst precursor, and calcining treatment is carried out on the catalyst precursor for 3 hours at 800 ℃ in air atmosphere to obtain 52 parts of catalyst product.
Example 2
60 parts of vesuvianite, 175 parts of absolute ethyl alcohol and 0.2 part of aluminum trichloride and 570 5 parts of silane coupling agent KH are added into an open container, stirring is carried out at room temperature, stirring is stopped after 2 hours, suction filtration is carried out, drying treatment is carried out at 110 ℃ for 2 hours in a drying oven to obtain a catalyst precursor, and calcining treatment is carried out on the precursor for 3 hours at 800 ℃ in air atmosphere to obtain 64 parts of catalyst product.
Example 3
70 parts of vesuvianite, 200 parts of absolute ethyl alcohol and 0.5 part of aluminum trichloride and 5 parts of silane coupling agent NXT are added into an open container, stirring is carried out at room temperature, stirring is stopped after 2 hours, suction filtration is carried out, drying treatment is carried out at 110 ℃ for 2 hours in a drying oven to obtain a catalyst precursor, and calcining treatment is carried out on the precursor for 3 hours at 800 ℃ in air atmosphere to obtain 73 parts of catalyst product.
Example 4
70 parts of 4A molecular sieve, 200 parts of absolute ethyl alcohol and 0.5 part of aluminum trichloride and 5 parts of silane coupling agent NXT are added into an open container, stirring is carried out at room temperature, stirring is stopped after 2 hours, suction filtration is carried out, drying treatment is carried out at 110 ℃ for 2 hours in a drying oven to obtain a catalyst precursor, and calcining treatment is carried out on the precursor for 3 hours at 800 ℃ in air atmosphere to obtain 72 parts of catalyst product.
Application example 1
105.14g (1 mol) of diethanolamine, 72.11g (1 mol) of isobutyraldehyde, 0.1g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of inert gas until no water generation was observed (about 2.5 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus 149.44g of compound (namely 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine) is obtained, and the yield is 93.85%. The LC-MS detection result is as follows, content 98.91%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 2
According to the reaction raw materials of diethanolamine and isobutyraldehyde of 1:1.5105.14g (1 mol) of diethanolamine, 108.16g (1.5 mol) of isobutyraldehyde, 0.1g of the catalyst of example 4, and 100mL of dried cyclohexane were charged into a reaction vessel equipped with a water separator and a reflux condenser, and the reaction temperature was controlled at 80℃and the reflux reaction was carried out under the protection of an inert gas until no water generation was observed (about 2.5 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus 152.86g of compound (namely 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine) is obtained, and the yield is 96.00%. The LC-MS detection result is as follows, the content is 99.74%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 3
105.14g (1 mol) of diethanolamine, 144.22g (2 mol) of isobutyraldehyde, 0.1g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2.5 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus 150.63g of compound (namely 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine) is obtained, and the yield is 94.6%. The LC-MS detection result is as follows, the content is 99.26%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 4
105.14g (1 mol) of diethanolamine, 180.27g (2.5 mol) of isobutyraldehyde, 0.1g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2.5 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus obtaining 156.72g of compound which is 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, and the yield is 98.41%. The LC-MS detection result is as follows, the content is 99.01%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 5
105.14g (1 mol) of diethanolamine, 216.33g (3 mol) of isobutyraldehyde, 0.1g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2.5 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus 156.38g of compound (namely 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine) is obtained, and the yield is 98.21%. The LC-MS detection result is as follows, content 98.97%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 6
105.14g (1 mol) of diethanolamine, 180.27g (2.5 mol) of isobutyraldehyde, 0.15g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2.2 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus obtaining 156.91g of compound which is 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, and the yield is 98.54%. The LC-MS detection result is as follows, the content is 99.01%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 7
105.14g (1 mol) of diethanolamine, 180.27g (2.5 mol) of isobutyraldehyde, 0.2g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus 157.64g of compound (namely 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine) is obtained, and the yield is 99.00%. LC-MS detection junctionThe content is 99.07%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 8
105.14g (1 mol) of diethanolamine, 180.27g (2.5 mol) of isobutyraldehyde, 0.25g of the catalyst of example 4 and 100mL of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a reaction temperature of 80℃under the protection of an inert gas until no water generation was observed (about 2 hours). After residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, the temperature is raised to 140 ℃ and reduced pressure distillation is carried out, thus obtaining 156.67g of compound which is 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, and the yield is 98.39%. The LC-MS detection result is as follows, the content is 98.85%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 9
10.514Kg (100 mol) of diethanolamine, 18.027Kg (250 mol) of isobutyraldehyde, 10g of the catalyst of example 4 and 10L of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a molar ratio of diethanolamine to isobutyraldehyde of 1:2.5, and the reaction temperature was controlled at 80℃and the reflux reaction was carried out under the protection of an inert gas until no formation of water was observed (about 3.5 hours). Evaporating residual moisture, solvent and low-boiling raw materials under reduced pressure, heating to 140 ℃ and performing reduced pressure distillation to obtain 15.672Kg of compound which is 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, wherein the yield is 98.42%. The LC-MS detection result is as follows, the content is 99.23%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 10
10.514Kg (100 mol) of diethanolamine, 18.027Kg (250 mol) of isobutyraldehyde, 20g of the catalyst of example 4 and 10L of dried cyclohexane were added to a reaction vessel equipped with a water separator and a reflux condenser at a molar ratio of diethanolamine to isobutyraldehyde of 1:2.5, and the reaction temperature was controlled at 80℃and the reflux reaction was carried out under the protection of an inert gas until no formation of water was observed (about 3.3 hours). Evaporating residual water, solvent and low-boiling raw material under reduced pressure, heating to 140deg.C, and reducingPressure distillation gave 15.670Kg of the compound, 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, in 98.41% yield. The LC-MS detection result is as follows, the content is 99.09%, MS + = 160.14. The product was a colorless transparent liquid.
Application example 11
1051.40Kg (10 kmol) of diethanolamine, 1802.70Kg (25 kmol) of isobutyraldehyde, 1.00Kg of the catalyst of example 4 and 1000L of dried cyclohexane are added into a jacketed reaction kettle with a mechanical stirring device, a reflux condensing device and a reflux receiving tank according to the mol ratio of the raw materials of diethanolamine and isobutyraldehyde of 1:2.5, the reaction temperature is controlled to 80 ℃, and the reflux reaction is carried out under the protection of inert gas until no water generation is observed (about 6.8 hours reaches the theoretical water yield). Evaporating residual moisture, solvent and low-boiling raw materials under reduced pressure, heating to 140 ℃ and performing reduced pressure distillation to obtain 1564.63Kg of compound which is 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, wherein the yield is 98.26%. The LC-MS detection result is as follows, the content is 99.02%, MS + = 160.14. The product was a colorless transparent liquid. The experiment is repeated for three batches, and the quality is stable.
Carrying out nuclear magnetic characterization on the obtained product, wherein the nuclear magnetic characterization conditions are as follows: the solvent is CDCl 3 The test temperature is 25 ℃, the instrument is a Bruce AVANCE III HD 600MHz nuclear magnetic resonance spectrometer, and the obtained nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum characterization result are shown in fig. 1 and 2. The corresponding data are as follows:
1 H NMR(600MHz,CDCl 3 )δ3.88(d,J＝5.2Hz,1H),3.75(t,J＝6.5Hz,2H),3.62–3.51(m,2H),3.12(dt,J＝10.4,6.3Hz,1H),2.98(s,1H),2.74(ddd,J＝12.9,8.2,4.9Hz,1H),2.61(dt,J＝10.3,6.6Hz,1H),2.49(dt,J＝12.5,4.4Hz,1H),1.63(dq,J＝13.4,6.7Hz,1H),0.90–0.81(m,6H).
13 C NMR(151MHz,CDCl 3 ) Delta 101.32,64.21,60.15,56.08,51.80,31.29,18.65,16.39 application example 12
13.319Kg (100 mol) of diisopropanolamine, 18.027Kg (250 mol) of isobutyraldehyde, 20g of the catalyst of example 4, and 10L of dried cyclohexane were added to a reactor with a water separator and returned in a molar ratio of diisopropanolamine to isobutyraldehyde of 1:2.5In the reaction kettle of the flow condensing device, the reaction temperature is controlled to be 80 ℃, and the reflux reaction is carried out under the protection of inert gas until no water generation is observed (about 2 hours). After the catalyst and the reaction liquid are separated by suction filtration, residual moisture, solvent and low-boiling raw materials are distilled off under reduced pressure, and the kettle liquid is yellowish clear liquid, and the purity of the liquid chromatography is 98.97%. Heating to 170 ℃ and carrying out reduced pressure distillation to obtain the target product 18.469Kg, 2-isopropyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine, wherein the yield is 98.62%. The LC-MS detection result is as follows, the content is 99.36%, MS + = 188.18. The product was a colorless transparent liquid. ( When diisopropanolamine participates in the reaction, if distillation is performed first, high-boiling impurities in the kettle are easy to form viscous coating on the catalyst, and the catalyst can not be recovered through solvent washing. Therefore, a post-treatment method of recovering the catalyst is adopted. )
Carrying out nuclear magnetic characterization on the obtained product, wherein the nuclear magnetic characterization conditions are as follows: the solvent is CDCl 3 The test temperature is 25 ℃, the instrument is a Bruce AVANCE III HD 600MHz nuclear magnetic resonance spectrometer, and the obtained nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum characterization result are shown in fig. 3 and 4. The corresponding data are as follows:
1 H NMR(400MHz,CDCl 3 )δ4.21–4.03(m,1H),3.99–4.03(m,1H),3.75–3.55(m,1H),3.49(s,1H),3.33–3.25(m,0.44H),2.91–2.66(m,0.65H),2.71–2.64–2.61(m,0.73H),2.46(dt,J＝22.6,7.5Hz,0.68H),2.38–2.20(m,1H),2.01(t,J＝8.9Hz,1H),1.75–1.49(m,1H),1.25–1.15(m,3H),1.15–1.05(m,3H),1.00–0.85(m,6H).
13 C NMR(100MHz,CDCl 3 )δ102.89,101.67,101.45,99.59,73.08,72.01,71.13,65.82,65.45,64.61,64.48,64.33,62.95,62.54,61.46,61.40,61.33,59.59,57.89,32.90,31.45,31.33,30.85,20.29,20.17,19.84,19.73,19.60,19.47,19.33,18.91,18.83,18.74,18.49,17.10,16.52,16.06,15.23.
application example 13
13.319Kg (100 mol) of diisopropanolamine, 18.027Kg (250 mol) of n-butyraldehyde, 20g of the catalyst of example 4 and drying are mixed according to the mol ratio of the diisopropanolamine to the n-butyraldehyde of 1:2.5The cyclohexane 10L was charged into a reaction vessel equipped with a water separator and a reflux condenser, and the reaction temperature was controlled at 80℃and the reflux reaction was carried out under the protection of an inert gas until no water generation was observed (about 2.2 hours). Filtering to remove the solid catalyst after cooling, carrying out post-treatment on the filtrate, and evaporating residual moisture, solvent and low-boiling raw materials under reduced pressure to obtain 18.526Kg of yellow oily compound which is 2-propyl-3- (2' -hydroxypropyl) -5-methyl-1, 3-oxazolidine, wherein the yield is 99.82%. The LC-MS detection result is as follows, the content is 99.23%, MS + = 160.14. And (3) injection: the yellow oily compound can be further refined by distillation under reduced pressure, and the fraction between 190 and 200 ℃ is collected under 6KPa, and the refined product is colorless transparent viscous liquid and can be solidified at room temperature.
Carrying out nuclear magnetic characterization on the obtained product, wherein the nuclear magnetic characterization conditions are as follows: the solvent is CDCl 3 The test temperature is 25 ℃, the instrument is a Bruce AVANCE III HD 600MHz nuclear magnetic resonance spectrometer, and the obtained nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum characterization result are shown in fig. 5 and 6.
13 C NMR(100MHz,CDCl 3 )δ96.41,64.02,60.03,55.01,51.60,36.16,30.60,21.88,18.24,14.25.
Application example 14
10.514Kg (100 mol) of diethanolamine, 18.027Kg (250 mol) of n-butyraldehyde, 20g of the catalyst of example 4 and 10L of dried cyclohexane are added into a reaction kettle with a water separator and a reflux condensing device according to the mol ratio of the raw materials of diethanolamine to n-butyraldehyde of 1:2.5, the reaction temperature is controlled to 80 ℃, and the reflux reaction is carried out under the protection of inert gas until no water generation is observed (about 3.3 hours). Evaporating residual water, solvent and low-boiling raw materials under the condition of 6KPa, heating to 165 ℃ and performing reduced pressure distillation to obtain 15.670Kg of compound which is 2-propyl-3-hydroxyethyl-1, 3-oxazolidine, wherein the yield is 98.41%. The LC-MS detection result is as follows, the content is 99.09%, MS + = 160.14. The product was a colorless transparent liquid. Catalyst can be recovered through solvent washing to high boiling, and the cyclic utilization of catalyst can be realized after drying.
Application example 15
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 4, except that: the catalyst used was the catalyst prepared in example 1. The yield of the obtained product was 92.16% and the content was 98.95%.
Application example 16
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 4, except that: the catalyst used was the catalyst prepared in example 2. The yield of the obtained product was 90.46% and the content was 99.01%.
Application example 17
2-propyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 13, except that: the catalyst used was the catalyst prepared in example 3. The yield of the obtained product was 88.66% and the content was 98.31%.
In view of the lewis acid nature of the catalyst prepared, the synthesis application of the Fischer indole is specially carried out, and the related Fischer indole synthesis reactions are all carried out in pressure-resistant bottles, and the application is as follows:
application example 18
108mg (1 mmol) of phenylhydrazine are dissolved in 5mL of toluene, followed by addition of 3mg of the catalyst prepared in the example and protection of the system with inert gas. 79mg (1.1 mmol) of n-butyraldehyde are added under inert gas, and the mixture is reacted at 110 ℃. Monitoring the reaction by adopting gas chromatography, filtering after the raw materials are converted, and concentrating the filtrate under reduced pressure to obtain the product 3-ethylindole. The yields of the corresponding products obtained when the catalysts of example 1, example 2, example 3, example 4 were used were 91.27%, 90.41%, 89.36%, 97.85%, respectively.
1 H NMR(400MHz,CDCl 3 )δ7.84(brs,1H)7.69-7.17(m,4H),6.96(s,1H),2.85(q,2H,J＝7.5Hz),1.38(t,3H,J＝7.5Hz).
13 C NMR(100MHz,CDCl 3 )δ136.31,127.44,121.82,120.40,119.06,118.71,111.03,18.27,14.42.
Application example 19
142mg (1.0 mmol) of p-chlorophenylhydrazine were dissolved in 5mL of toluene, followed by the addition of 3mg of the catalyst prepared in the example and the inert gas protection of the system. 79mg (1.1 mmol) of n-butyraldehyde are added under inert gas, and the mixture is reacted at 110 ℃. The reaction was monitored by gas chromatography, after the conversion of the raw materials was completed, the filtration was carried out, the filtrate was concentrated under reduced pressure to obtain a crude product, and the column chromatography was carried out to obtain 3-ethyl-5-chloroindole as a product, and the yields of the corresponding products obtained by the catalysts of example 1, example 2, example 3 and example 4 were 89.63%, 87.78%, 81.35% and 88.18%, respectively.
1 H NMR(400MHz,CDCl 3 )δ7.95(brs,1H),7.59(d,J＝2.0Hz,1H),7.27(d,J＝8.6Hz,1H),7.15(dd,J＝8.6,2.0Hz,1H),7.01(s,1H),2.76(q,J＝7.6Hz,2H),1.34(t,J＝7.6Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ134.74,128.58,124.81,122.13,121.89,118.64,118.49,112.01,18.20,14.37.
Application example 20
186mg (1.0 mmol) of p-bromophenylhydrazine are dissolved in 5mL of toluene, and 3mg of the catalyst prepared in the example is added and the system is under inert gas. 95mg (1.1 mmol) of isovaleraldehyde are added under inert gas, and the mixture is reacted at 110 ℃. The reaction was monitored by gas chromatography, after the conversion of the raw materials was completed, the filtration was carried out, the filtrate was concentrated under reduced pressure to obtain a crude product, and the column chromatography was carried out to obtain 3-isopropyl-5-bromoindole as a product, and the yields of the corresponding products obtained by the catalysts of example 1, example 2, example 3 and example 4 were 87.64%, 86.73%, 80.14% and 88.09%, respectively.
1 H NMR(400MHz,CDCl 3 )δ8.72(s,1H),8.57(s,1H),8.05(m,2H),7.77(s,1H),3.95(m,1H),2.15(d,J＝6.6Hz,6H).
Application example 21
142mg (1.0 mmol) of p-chlorophenylhydrazine were dissolved in 5mL of toluene, followed by the addition of 3mg of the catalyst prepared in the example and the inert gas protection of the system. 95mg (1.1 mmol) of valeraldehyde are added under inert gas, and the mixture is reacted at 110 ℃. The reaction was monitored by gas chromatography, after the conversion of the raw materials was completed, the filtration was carried out, the filtrate was concentrated under reduced pressure to obtain a crude product, and the column chromatography was carried out to obtain 3-propyl-5-bromoindole as a product, and the yields of the corresponding products obtained by the catalysts of example 1, example 2, example 3 and example 4 were 63.57%, 64.01%, 59.47% and 78.59%, respectively.
1 H NMR(400MHz,CDCl 3 )δ7.99(brs,1H),7.59(d,J＝1.7Hz,1H),7.27(d,J＝8.4Hz,1H),7.15(dd,J＝8.6,1.8Hz,1H),7.01(s,1H),2.71(t,J＝7.4Hz,2H),1.74(m,2H),1.02(t,J＝7.4Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ134.69,128.81,124.80,122.58,122.05,118.56,116.78,112.01,27.13,23.28,14.12.
The catalyst can effectively realize the synthesis of target products, and for comparison with the existing process and method, the following comparative examples are specially implemented, wherein all the adopted methods are carried out according to methods reported in documents or patents, and the catalyst disclosed by the invention is not used, and the specific information is as follows:
comparative example 1
Experiments were performed according to the procedure reported in CN 105111158A.
0.5mol of diethanolamine and 100ml of benzene are taken and added into a 500ml four-necked flask with a reflux and water diversion device, the temperature is raised to 40 ℃, 0.2mol of isobutyraldehyde is added under stirring, and the temperature is slowly raised to reflux (75 ℃ in the original document, higher than 97 ℃ in the practical experiment process). After water separation is completed, the product is distilled under reduced pressure under 0.095MPa to collect fraction at 135 ℃ to obtain yellowish viscous liquid, namely the product. The yields of the three parallel reactions were 65.95%, 65.06%, 65.91% (67.7% of the original document yield), respectively, and the toluene taste was rich (gas chromatography showed toluene residues and could not be removed by work-up). And (3) injection: the equipment used for the reduced pressure distillation is a diaphragm pump. With this method, the reaction of diethanolamine with n-butyraldehyde was attempted with similar results. The reaction of diisopropanolamine and isobutyraldehyde is tried, separation of raw materials and products cannot be realized, and the raw materials and the products have stronger toluene smell.
Comparative example 2
According to document "Zhang Ping et al: 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine synthesis and structural characterization, methods reported by the university of western security, university of ethnicity (natural science edition), 2006, 32 (3), 529-532 "were used for the experiments.
24mL (0.25 mol) of diethanolamine and 20mL of cyclohexane are added into a 150mL three-necked flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, 22.4mL (0.25 mol) of isobutyraldehyde is added dropwise under stirring, the temperature is controlled to be not higher than 50 ℃, the temperature is kept for 0.5h after the addition is completed, and then the dropping funnel is changed into a water separator. After completion of the water separation (about 4.5 hours), the solution was cooled to room temperature, and the fraction of 146 ℃ C./80 mmHg was collected by distillation under reduced pressure, and the yields of the three experiments were 66.07%, 66.96% and 66.45%, respectively (the yield of 74.2% was reported in the literature). And (3) injection: the equipment used for the reduced pressure distillation is a common water circulating pump in a laboratory. With this method, the reaction of diethanolamine with n-butyraldehyde was attempted with similar results. The reaction of diisopropanolamine with isobutyraldehyde cannot be achieved.
Comparative example 3
The reactions were performed in parallel three times according to the methods reported in documents such as JP 200888220, JP2009119358, JP2008222792, JP2009067917, JP2016145321, etc.
Toluene is adopted as a water carrying agent. When the reaction temperature is 60-130 ℃, a dark red product (not reported in the literature) is obtained after post-treatment by adopting a method reported in the literature, and the purity of the crude product is lower; when the reaction temperature is 110-150 ℃, the raw material diethanolamine is remained, the raw material diethanolamine cannot be completely converted, the purity is low, and the mixed liquor is reddish brown after the post-treatment (not reported in the literature). And (3) injection: the equipment used for the reduced pressure distillation is a common water circulating pump in a laboratory. By adopting the method, the reaction of diethanolamine and n-butyraldehyde and the reaction of diisopropanolamine and isobutyraldehyde are tried, and the yield is lower than 47%.
Comparative example 4
According to the method reported in document "Izvestiya Natsional' noi Akademii Nauk Respubliki Kazakhstan, seriya Khimicheskaya,2007, (2), 40-44" the reaction is carried out using microwaves as a heat source.
The microwave-assisted synthesis extraction instrument manufactured by the swan technology Co., ltd is adopted, the heating temperature is respectively set to 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, and the setting temperature is respectively set to 10min, 15min, 20min, 25min and 30min. Liquid chromatography showed that the highest content of the reaction product was 76.4% (not reported in the literature), the color was tan (not reported in the literature), and the corresponding reaction conditions were 110℃for 25min. Because the separation of water and the system cannot be realized in the reaction process, the subsequent hydrolysis is serious. After natural cooling for 15min, liquid chromatography showed a decrease in product content of 64.03% without further separation analysis. With this method, the reaction of diethanolamine with n-butyraldehyde was attempted with similar results. The reaction of diisopropanolamine with isobutyraldehyde cannot be achieved.
Comparative example 5
According to the method reported in the document "Eur. Pat. Appl.,414962", benzene was used as a solvent, diisopropanolamine was reacted with isobutyraldehyde, the heating temperature was set to 70℃and 80℃and 90℃respectively, and liquid chromatography showed that the highest content of the reaction product was 69.9%, and no further separation analysis was performed. With this method, the reaction of diethanolamine with n-butyraldehyde was attempted with similar results.
Comparative example 6
According to the document CN202011641642.1, the reaction is carried out in a mode of excessive diethanolamine, 90 parts by mass of diethanolamine and 100 parts by mass of cyclohexane serving as an organic solvent are added into a reaction kettle, the mixture is uniformly stirred and heated to 50 ℃,60 parts by mass of isobutyraldehyde is added dropwise, and the reaction is carried out for 0.5 hour at a constant temperature; reflux water diversion is carried out when the temperature of the reaction kettle is raised to 75 ℃ and the water diversion time is 4 hours, and the material liquid is cooled to room temperature and then heated to evaporate the organic solvent for recycling; the separated feed solution was subjected to vacuum fractionation, and a fraction at 120℃was collected under a vacuum of 60Pa, whereby 86 parts by mass (90 parts by mass in three repetitions) of 2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine, which was a colorless transparent liquid, was obtained (130 parts by mass was reported in the literature). When toluene is used as a water-carrying agent, the diethanolamine reaction can not be completely converted, and the toluene remained in the product can not be completely converted. The reaction of diethanolamine with n-butyraldehyde cannot be realized.
Comparative example 7
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 4, except that: the catalyst used was a powdered 4A molecular sieve, which was not modified. The yield of the obtained product was 78.11% and the purity was 96.66%.
Comparative example 8
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared according to the method of application example 15, except that: the catalyst used was the catalyst of example 1 except that the silane coupling agent KH580 was replaced with the silane coupling agent KH550 when the catalyst was prepared. The yield of the obtained product was 86.91% and the purity was 97.99%.
Comparative example 9
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 4, except that: the catalyst used was the catalyst of example 4 except that ferric chloride was used in place of aluminum chloride in the original feed in the preparation of the catalyst. The yield of the obtained product was 80.66% and the purity was 97.98%.
Comparative example 10
2-isopropyl-3-hydroxyethyl-1, 3-oxazolidine was prepared as in application example 4, except that: the catalyst used was p-toluene sulfonic acid. The yield of the obtained product was 77.95% and the purity was 97.66%.
Catalyst recovery performance verification
The treatment method comprises the following steps: washing the recovered catalyst particles with ethyl acetate under the suction filtration condition until the filtrate is colorless; drying overnight at 50 ℃ in the oven, and recycling the obtained catalyst.
The recovered catalyst was recycled according to the methods of application example 7 and application example 18, except that the catalyst used was a catalyst recycled for various times, and the specific results are shown in tables 1 and 2 below:
TABLE 1
TABLE 2
In summary, the experiment shows that the amplification reaction is implemented, namely, when the mass ratio of diethanolamine to isobutyraldehyde is 1:2.5 and the catalyst addition amount is 1Kg, the conversion rate of the reaction raw materials is highest, meanwhile, the moisture and the impurities are the least, repeated experiments show that the product produced by the process is stable in quality, the prepared hydroxy oxazolidine is optimal, and the application prospect in the application fields of polyurethane systems and waterproof coatings is great. Meanwhile, the process condition is also suitable for preparing the hydroxy oxazolidine derivative by reacting diisopropanolamine with isobutyraldehyde and n-butyraldehyde, and diethanolamine with n-butyraldehyde. The recycling performance verification after catalyst recovery shows that the catalyst can be recycled and the performance is kept unchanged. In addition, the catalyst maintains the characteristics of Lewis acid, can effectively catalyze Fischer indole synthesis, and has excellent catalytic activity and wide application prospect in the field.
As can be seen from comparative examples 1 to 6, the products prepared by the conventional experimental method have higher chromaticity, the raw materials cannot realize high conversion rate, the purity of the final products is lower, the application fields with high chromaticity requirements are difficult to apply, and the large-scale preparation, especially the microwave-assisted method, is difficult to realize. From the comparison example, the catalyst adopted in the invention greatly promotes the reaction, and has the characteristics of saving energy consumption and obviously shortening the production period; meanwhile, the hydroxy oxazolidine prepared by the process can obtain a high-purity colorless clear product in a distillation mode, and has a wide application prospect.
As can be seen from the comparison of comparative examples 7-10 with the examples, the catalyst of the present invention obtained by the specific method can greatly improve the yield of the hydroxy oxazolidine.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (10)

1. The preparation method of the supported catalyst is characterized by comprising the following steps:
(1) Mixing porous material, aluminum trichloride, silane coupling agent and solvent for reaction;
(2) And (3) filtering and drying after the reaction, and calcining the obtained catalyst precursor to obtain the supported catalyst.
2. The preparation method according to claim 1, characterized in that: in the step (1), the following raw materials are used in parts by weight: 50-70 parts of porous material, 0.1-2.0 parts of aluminum trichloride and 1-10 parts of silane coupling agent.
3. The preparation method according to claim 1 or 2, characterized in that: in the step (1), the silane coupling agent is a silane coupling agent KH570, a silane coupling agent KH580 or a silane coupling agent NXT.
4. The preparation method according to claim 1 or 2, characterized in that: in the step (1), the porous material is a porous inorganic compound, preferably a vesuvianite or a molecular sieve, and the molecular sieve is a 3A type molecular sieve, a 4A type molecular sieve or a 5A type molecular sieve.
5. The preparation method according to claim 1 or 2, characterized in that: in the step (1), the porous material and the solvent are mixed, then the temperature is controlled to be 10-80 ℃, and aluminum trichloride and the silane coupling agent are added under stirring to carry out modification reaction; preferably, the reaction time is 20 to 200 minutes; in the step (2), the calcination temperature is 700-880 ℃, and the calcination time is 2-8h.
6. A supported catalyst produced by the process for producing a supported catalyst according to any one of claims 1 to 5.
7. The use of the supported catalyst of claim 6 for the preparation of a hydroxyoxazolidine or indole compound.
8. A preparation method of hydroxyl oxazolidine is characterized by comprising the following steps: the method comprises the steps of reacting diethanolamine and derivatives thereof with aldehyde serving as a substrate and the supported catalyst of claim 6 serving as a catalyst under the protection of gas to obtain the hydroxyl oxazolidine.
9. The method for preparing the composite material according to claim 8, wherein: the diethanolamine and the derivative thereof are diethanolamine or diisopropanolamine; the aldehyde is isobutyraldehyde or n-butyraldehyde; preferably, the molar ratio of diethanolamine and its derivatives to aldehyde is 1: 1-3, more preferably 1:2.5; preferably, 0.1g to 0.25g of catalyst is added per 1mol of diethanolamine and derivatives thereof.
10. The method for preparing the composite material according to claim 8, wherein: the reaction is carried out in an organic solvent; and (3) raising the temperature to reflux temperature for reaction, wherein the reaction time is 2-8h, and continuously separating out generated water.
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