Preparation method of amine compound

Abstract

The invention discloses a preparation method of an amine compound, which comprises the following steps: reacting an aldehyde ketone substrate with ammonia water in a solvent under the conditions of a catalyst and hydrogen to generate the amine compound, wherein the catalyst comprises a zirconium-tungsten composite carrier and ruthenium loaded on the zirconium-tungsten composite carrier; the method can be used for preparing primary amine through one-step catalysis of aldehyde ketone amination, the reaction temperature and pressure are low, ammonia water is used as a nitrogen source, and the condition is mild; in addition, the yield is relatively high, and industrial application is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of fine chemistry, in particular to amination conversion of aldehydes and ketones, and specifically to a method for preparing amine compounds. Background Art

[0002] Amine compounds are an indispensable component in the chemical industry and life sciences. They have good nucleophilic properties and are widely used in industrial production such as pharmaceuticals, agricultural chemicals, polymers, food additives, and surfactants. The current methods for preparing amine compounds include: (1) using aqueous ammonia as a nitrogen source and a catalyst to catalyze the reductive amination reaction of furfural; however, the yield of the target product using aqueous ammonia as a nitrogen source is generally low, and a higher hydrogen pressure is required; (2) using ammonia gas instead of aqueous ammonia as a nitrogen source, using a catalyst to aminate a number of aldehydes and ketones and obtain the target amine compound, however, ammonia gas has certain dangers, and the simultaneous introduction of a certain pressure of hydrogen and ammonia gas places high demands on the reaction equipment. Therefore, finding a method that can increase the yield of the amination product under mild conditions has become a technical problem that needs to be solved in this field.

[0003] It should be noted that the information disclosed in the above background technology section is only used to understand the background of the present application, so the background technology section of the present invention may contain background information about the problem or environment of the present invention, but not necessarily describe the prior art. Therefore, the content contained in the background technology section is not an admission of the applicant to the prior art. Summary of the invention

[0004] The purpose of the present invention is to overcome one or more deficiencies in the prior art and to provide a new method for preparing amine compounds with high efficiency and high yield under milder conditions.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing an amine compound comprises: reacting an aldehyde ketone substrate and ammonia water in a solvent under the conditions of a catalyst and hydrogen to generate an amine compound; wherein the catalyst comprises a zirconium-tungsten composite carrier and ruthenium loaded on the zirconium-tungsten composite carrier.

[0007] In some embodiments of the present invention, the aldehyde-ketone substrate has a structure shown in formula (I):

[0008] The amine compound has a structure shown in formula (II):

[0009] In formula (I) and formula (II), R1 and R2 are independently selected from H, or independently selected from the following substituted or unsubstituted groups: saturated heterocyclic group, unsaturated heterocyclic group, carbocyclic aromatic group, carbocyclic aromatic group C 1-10 Alkyl, unsaturated heterocyclic group C 1-10 Alkyl; the substituted substituents are selected from one or more of the following groups: C 1-10 Alkyl, hydroxyl C 1-10 Alkyl, C 1-10 Alkoxy, halogen, C 1-10 Alkoxycarbonyl, -NR a R b , Carbocyclic aromatic group, carbocyclic aromatic group C 1-10 Alkoxy, hydroxyl, R a , R b Independently selected from H, C 1-10 alkyl;

[0010] R1 and R2 are not H at the same time;

[0011] Alternatively, R1 and R2 are connected to form a 3-12 membered carbocyclic ring with the carbon atom to which they are connected;

[0012] The saturated heterocyclic group, the unsaturated heterocyclic group, the unsaturated heterocyclic group C 1-10 The heteroatom in the alkyl group is selected from one or more of O, N and S.

[0013] In some embodiments of the present invention, R1 is selected from H, and R2 is selected from the following substituted or unsubstituted groups:

[0014] Where X is O, NH or S, Y is CH or N, R c Selected from C 1-10 Alkyl, R d Selected from C 1-10 alkyl.

[0015] In some embodiments of the present invention, R2 is selected from

[0016] R3 is selected from H, hydroxyl C 1-6 Alkyl or C 1-6 Alkyl, R4, R5 are independently selected from H, C 1-6 Alkyl, fluorine, chlorine, bromine, C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, -N(CH3)CH3 or R6 is selected from C 1-6 Alkyl, fluorine, chlorine, bromine or C1-6 Alkoxy; m is 1-6, t is 1-3.

[0017] In some embodiments of the present invention, R2 is selected from

[0018] In some embodiments of the present invention, R1 and R2 are connected to form a 5-7 membered carbon ring with the carbon atom they are connected to, and can further be a 6-membered ring.

[0019] In some embodiments of the present invention, the reaction is carried out at 60-120°C, further at 60-100°C.

[0020] In some embodiments of the present invention, for every 1 mmol of aldehyde and ketone substrates, the amount of ammonia water added is 0.5-1.5 mL, and the mass concentration of ammonia water is 25%-28%.

[0021] In some embodiments of the present invention, the solvent is an organic solvent, the organic solvent includes an alcohol compound, and the alcohol compound includes isopropanol.

[0022] In some embodiments of the present invention, the pressure of the hydrogen is controlled to be 0.5-1.5 MPa.

[0023] In some embodiments of the present invention, for every 1 mmol of aldehyde and ketone substrates, the amount of the catalyst added is 25-35 mg, and the amount of the solvent added is 4-6 mL.

[0024] In some embodiments of the present invention, in the zirconium-tungsten composite carrier, the molar ratio of the zirconium to the tungsten is 8-32:1, further 15-18:1, for example, 16:1, 17:1, etc.

[0025] In some embodiments of the present invention, in the zirconium-tungsten composite carrier, the molar ratio of the zirconium to the tungsten is 14-29:1, further 14-22.5:1, and further 16-18.5:1.

[0026] In some embodiments of the present invention, the catalyst is prepared by the following method:

[0027] (1) dispersing ammonium metatungstate and zirconium nitrate in water, adjusting the system to be alkaline, reacting under heating conditions, separating solids, and then calcining in an air atmosphere to obtain a zirconium-tungsten composite carrier;

[0028] (2) The zirconium-tungsten composite carrier and the ruthenium source are dispersed in water, urea is added, and the mixture is reacted under heating conditions. The solid is separated and then calcined in a protective atmosphere and a hydrogen atmosphere in sequence.

[0029] In some embodiments of the present invention, in step (1), the zirconium nitrate is used as a raw material in the form of zirconium nitrate pentahydrate.

[0030] In some embodiments of the present invention, in step (1), the pH value of the system is adjusted to 9.5-10.5 by adding ammonia water.

[0031] In some embodiments of the present invention, in step (1), the feed mass ratio of the ammonium metatungstate to the zirconium nitrate pentahydrate is 25-50:1, further 25-40:1, and further 25-35:1.

[0032] In some embodiments of the present invention, in step (1), the heating conditions are controlled so that the reaction temperature is 70-90°C.

[0033] In some embodiments of the present invention, in step (1), the calcination temperature is 500-600°C.

[0034] In some embodiments of the present invention, in step (1), the heating rate of the calcination is controlled to be 1-10°C / min, further 2-8°C / min, and further 4-6°C / min.

[0035] In some embodiments of the present invention, in step (1), the calcination time is controlled to be 1-10 hours, further 3-6 hours.

[0036] In some embodiments of the present invention, in step (2), the ruthenium source is a ruthenium halide, further, the ruthenium halide includes ruthenium trichloride, and further, the ruthenium trichloride is used as a raw material in the form of RuCl3·H2O.

[0037] In some embodiments of the present invention, in step (2), the feed mass ratio of the ruthenium source, the zirconium-tungsten composite support and the urea is 1:40-50:40-50.

[0038] In some embodiments of the present invention, in step (2), the ruthenium source and the urea are added in the form of aqueous solutions respectively.

[0039] In some embodiments of the present invention, in step (2), the heating conditions are controlled so that the reaction temperature is 70-90°C.

[0040] In some embodiments of the present invention, in step (2), the protective atmosphere is a nitrogen atmosphere or an inert gas atmosphere.

[0041] In some embodiments of the present invention, in step (2), the calcination under a protective atmosphere is controlled to be carried out at 450-550°C, and further, the heating rate is controlled to be 1-10°C / min, further to 2-8°C / min, and further to 4-6°C / min.

[0042] In some embodiments of the present invention, in step (2), the calcination time under a protective atmosphere is controlled to be 1-6 hours, further 2-4 hours.

[0043] In some embodiments of the present invention, in step (2), the calcination in hydrogen atmosphere is controlled to be carried out at 350-450°C, and further, the heating rate is controlled to be 1-10°C / min, further to 2-8°C / min, and further to 4-6°C / min.

[0044] In some embodiments of the present invention, in step (2), the calcination time in hydrogen atmosphere is controlled to be 1-6 hours, further 2-4 hours.

[0045] The reaction mechanism of the present invention is roughly as follows:

[0046]

[0047] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0048] The present invention is based on a large number of experimental studies and unexpectedly discovered that the catalyst formed by ruthenium loaded on a zirconium-tungsten composite carrier can catalyze the amination of aldehydes and ketones to prepare primary amines in one step, and the reaction temperature and pressure are low, and ammonia water is used as the nitrogen source, and the conditions are mild; in addition, the yield is relatively high, all above 80%, which is conducive to industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 Gas chromatography-mass spectrometry of the product after the reaction of Example 2 of the present invention;

[0050] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of Example 13 of the present invention;

[0051] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of Example 15 of the present invention;

[0052] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of Example 18 of the present invention;

[0053] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of Example 19 of the present invention. DETAILED DESCRIPTION

[0054] The above scheme is further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments; the implementation conditions adopted in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0055] Unless otherwise specified in the following examples, all raw materials are commercially available or prepared by conventional methods in the art.

[0056] Example 1: Preparation of Ru / 16ZrW catalyst

[0057] (1) 9 g of zirconium nitrate pentahydrate was dissolved in 20 mL of water, and 0.3 g of ammonium metatungstate was dissolved in 5 mL of water. The two were mixed and stirred for 30 min, and then ammonia water (mass concentration was 26%) was added to adjust the pH value of the system to 10, and the stirring was continued for 30 min. After the stirring was completed, it was placed at room temperature for 2 h, and then placed in a constant temperature water bath at 80 ° C and stirred for 4 h. After the reaction was completed, it was centrifuged, washed with deionized water, and dried. In an atmosphere with air, the temperature was increased to 550 ° C at a heating rate of 5 ° C / min, and constant temperature calcined for 4 h to obtain a zirconium-tungsten composite carrier.

[0058] (2) RuCl3·H2O and urea were dissolved in water to prepare 10 mg / mL RuCl3·H2O solution and 15 mg / mL urea aqueous solution, and then 0.6 g zirconium-tungsten composite carrier was dispersed in 40 mL water, and 1.34 mL RuCl3·H2O solution was added thereto under stirring at room temperature, and stirred for 30 min. Then 40 mL urea aqueous solution was added, and the mixture was placed in a constant temperature water bath at 80°C and stirred for 4 h. After the reaction was completed, the mixture was centrifuged, washed with deionized water, and dried. In an atmosphere of nitrogen, the temperature was increased to 500°C at a heating rate of 5°C / min, and the mixture was calcined at a constant temperature for 3 h. Then, the temperature was increased to 400°C at a heating rate of 5°C / min in an atmosphere of hydrogen, and the mixture was calcined at a constant temperature for 3 h to obtain the catalyst Ru / 16ZrW.

[0059] Example 2: One-step catalytic amination of furfural to prepare furfuralamine

[0060] Reaction:

[0061] 96 mg (1 mmol) of furfural, 30 mg of Ru / 16ZrW, 1 mL of aqueous ammonia and 5 mL of isopropanol were added to a high-pressure reactor, and hydrogen was replaced three times. The hydrogen pressure was controlled at 1 MPa, and the reaction was stirred at 80° C. (rotation speed 800 rpm) for 6 hours. After the reaction was completed, the solution was diluted with ethyl acetate, the catalyst was separated by centrifugation, and the water in the solution was removed with anhydrous sodium sulfate. Chlorobenzene was used as an internal standard, and the yield of the target product furfuralamine was determined to be 99% by gas chromatography-mass spectrometry.

[0062] Example 3: One-step catalytic amination of 5-hydroxymethylfurfural to prepare 5-(aminomethyl)-2-furanmethanol

[0063] Reaction:

[0064] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 126 mg (1 mmol) of 5-hydroxymethylfurfural. The reaction result was that the yield of the target product 5-(aminomethyl)-2-furanmethanol was 99%.

[0065] Example 4: One-step catalytic amination of 5-methylfurfural to prepare 5-methylfurfurylamine

[0066] Reaction:

[0067] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 110 mg (1 mmol) of 5-methylfurfural. The reaction result was that the yield of the target product 5-methylfurfural was 99%.

[0068] Example 5: One-step catalytic amination of benzaldehyde to prepare benzylamine

[0069] Reaction:

[0070] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 106 mg (1 mmol) of benzaldehyde, the reaction temperature was 100° C., and the reaction result was that the yield of the target product benzylamine was 84%.

[0071] Example 6: One-step catalytic amination of phenylpropionaldehyde to prepare 3-amphetamine

[0072] Reaction:

[0073] Other parts are the same as in Example 2, except that the aldehyde-ketone substrate added is 134 mg (1 mmol) of phenylpropionaldehyde, and the reaction result is that the productive rate of the target product 3-amphetamine is 99%.

[0074] Example 7: One-step catalytic amination of p-methylbenzaldehyde to prepare 4-methylbenzylamine

[0075] Reaction:

[0076] The other parts were the same as Example 2, except that the added aldehyde and ketone substrate was 120 mg (1 mmol) of p-methylbenzaldehyde, the reaction temperature was 100° C., and the reaction result was that the yield of the target product 4-methylbenzylamine was 96%.

[0077] Example 8: One-step catalytic amination of p-tert-butylbenzaldehyde to prepare 4-tert-butylbenzylamine

[0078] Reaction:

[0079] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 162 mg (1 mmol) of p-tert-butylbenzaldehyde. The reaction result was that the yield of the target product 4-tert-butylbenzylamine was 92%.

[0080] Example 9: One-step catalytic amination of 4-chlorobenzaldehyde to prepare 4-chlorobenzylamine

[0081] Reaction:

[0082] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 141 mg (1 mmol) of 4-chlorobenzaldehyde. The reaction result was that the yield of the target product 4-chlorobenzylamine was 99%.

[0083] Example 10: One-step catalytic amination of p-methoxybenzaldehyde to prepare 4-methoxybenzylamine

[0084] Reaction:

[0085] The other parts were the same as Example 2, except that the added aldehyde and ketone substrate was 136 mg (1 mmol) of p-methoxybenzaldehyde, the reaction temperature was 100° C., and the reaction result was that the yield of the target product 4-methoxybenzylamine was 86%.

[0086] Example 11: One-step catalytic amination of methyl p-formylbenzoate to prepare methyl 4-(aminomethyl)benzoate

[0087] Reaction:

[0088] The other parts are the same as Example 2, except that the added aldehyde ketone substrate is 164 mg (1 mmol) of methyl p-formylbenzoate, the reaction temperature is 100° C., and the reaction result is that the yield of the target product 4-(aminomethyl)benzoic acid methyl ester is 85%.

[0089] Example 12: One-step catalytic amination of p-dimethylaminobenzaldehyde to prepare 4-dimethylaminobenzylamine

[0090] Reaction:

[0091] The other parts are the same as Example 2, except that the added aldehyde and ketone substrate is 149 mg (1 mmol) of p-dimethylaminobenzaldehyde, the reaction temperature is 100° C., and the reaction result is that the yield of the target product 4-dimethylaminobenzylamine is 98%.

[0092] Example 13: One-step catalytic amination of 4-formylphenylboronic acid pinacol ester to prepare 4-(aminomethyl)phenylboronic acid pinacol ester

[0093] Reaction:

[0094] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 232 mg (1 mmol) of 4-formylphenylboronic acid pinacol ester, and the reaction result was that the yield of the target product 4-(aminomethyl)phenylboronic acid pinacol ester was 99%.

[0095] After that, the solvent in the solution was evaporated to dryness, and 10 mL of ether, 2 mL of hydrochloric acid, and 5 mL of methanol were added in sequence, and stirred at room temperature for 4 h. After the stirring was completed, the solvent in the solution was evaporated to dryness, 10 mL of ethyl acetate was added, and stirred at room temperature for 30 min, and filtered to obtain the ammonium salt form of the target product, and deuterated dimethyl sulfoxide was used as the solvent for nuclear magnetic resonance analysis. The nuclear magnetic resonance hydrogen spectrum is shown in Figure 2 shown.

[0096] Example 14: One-step catalytic amination of 4-biphenylformaldehyde to prepare 4-phenylbenzylamine

[0097] Reaction:

[0098] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 182 mg (1 mmol) of 4-biphenylaldehyde. The reaction result was that the yield of the target product 4-phenylbenzylamine was 99%.

[0099] Example 15: One-step catalytic amination of 4-benzyloxybenzaldehyde to prepare 4-benzyloxybenzylamine

[0100] Reaction:

[0101] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 212 mg (1 mmol) of 4-benzyloxybenzaldehyde. The reaction result was that the yield of the target product 4-benzyloxybenzylamine was 99%.

[0102] Then, under the same feed mass and reaction conditions as in Example 13, the target product was converted into an ammonium salt form, and NMR analysis was performed using deuterated dimethyl sulfoxide as solvent. The H NMR spectrum is shown in Figure 3 shown.

[0103] Example 16: One-step catalytic amination of vanillin to prepare 4-(aminomethyl)-2-methoxyphenol

[0104] Reaction:

[0105] The other parts were the same as Example 2, except that the added aldehyde and ketone substrate was 152 mg (1 mmol) of vanillin, the reaction temperature was 100° C., and the reaction result was that the yield of the target product 4-(aminomethyl)-2-methoxyphenol was 99%.

[0106] Example 17: One-step catalytic amination of veratraldehyde to prepare 3,4-dimethoxybenzylamine

[0107] Reaction:

[0108] The other parts were the same as Example 2, except that the added aldehyde and ketone substrate was 166 mg (1 mmol) of veratraldehyde, the reaction temperature was 100° C., and the reaction result was that the yield of the target product 3,4-dimethoxybenzylamine was 93%.

[0109] Example 18: One-step catalytic amination of 1,4-benzodioxane-6-carboxaldehyde to prepare 2,3-dihydro-1,4-benzodioxetane-6-methylamine

[0110] Reaction:

[0111] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 164 mg (1 mmol) of 1,4-benzodioxane-6-carboxaldehyde, and the reaction result was that the yield of the target product 2,3-dihydro-1,4-benzodioxetane-6-methylamine was 93%.

[0112] Then, under the same feed mass and reaction conditions as in Example 13, the target product was converted into an ammonium salt form, and NMR analysis was performed using deuterated dimethyl sulfoxide as solvent. The H NMR spectrum is shown in Figure 4 shown.

[0113] Example 19: One-step catalytic amination of 2-methyl-3-(3,4-methylenedioxyphenyl)-propanal to prepare 2-methyl-3-(3,4-methylenedioxyphenyl)-propylamine

[0114] Reaction:

[0115] The other parts are the same as Example 2, except that the added aldehyde and ketone substrate is 192 mg (1 mmol) of 2-methyl-3-(3,4-methylenedioxyphenyl)-propanal, and the reaction result is that the yield of the target product 2-methyl-3-(3,4-methylenedioxyphenyl)-propylamine is 99%.

[0116] Then, under the same feed mass and reaction conditions as in Example 13, the target product was converted into an ammonium salt form, and NMR analysis was performed using deuterated dimethyl sulfoxide as solvent. The H NMR spectrum is shown in Figure 5 shown.

[0117] Example 20: One-step catalytic amination of 3-pyridinecarboxaldehyde to prepare 3-aminomethylpyridine

[0118] Reaction:

[0119] The other parts were the same as Example 2, except that the aldehyde and ketone substrate added was 107 mg (1 mmol) of 3-pyridinecarboxaldehyde, the reaction temperature was 100° C., and the reaction result was that the yield of the target product 3-aminomethylpyridine was 99%.

[0120] Example 21: One-step catalytic amination of 1-naphthaldehyde to prepare 1-naphthylamine

[0121] Reaction:

[0122] The other parts are the same as Example 2, except that the added aldehyde and ketone substrate is 156 mg (1 mmol) of 1-naphthaldehyde, the reaction temperature is 100° C., and the reaction result is that the yield of the target product 1-naphthylamine is 94%.

[0123] Example 22: One-step catalytic amination of 6-methoxy-2-naphthaldehyde to prepare 6-methoxy-2-naphthylamine

[0124] Reaction:

[0125] The other parts are the same as Example 2, except that the aldehyde and ketone substrate added is 186 mg (1 mmol) of 6-methoxy-2-naphthaldehyde. The reaction result is that the yield of the target product 6-methoxy-2-naphthylamine is 99%.

[0126] Example 23: One-step catalytic amination of cyclohexanone to produce cyclohexylamine

[0127] Reaction:

[0128] The other parts were the same as Example 2, except that the added aldehyde and ketone substrate was 98 mg (1 mmol) of cyclohexanone, the reaction temperature was 100° C., and the reaction result was that the yield of the target product cyclohexylamine was 99%.

[0129] Example 24: Repeated use of Ru / 16ZrW to catalyze the amination of furfural to prepare furfuralamine

[0130] 96 mg (1 mmol) furfural, 30 mg Ru / 16ZrW, 1 mL ammonia water, 5 mL isopropanol were added to a high pressure reactor, hydrogen was replaced three times, the hydrogen pressure was controlled at 1 MPa, and the reaction was stirred at 80°C (rotation speed 800 rpm) for 6 h; after the reaction was completed, it was diluted with ethyl acetate, the catalyst was separated by centrifugation, washed with water three times and dried. The above process was repeated 10 times, anhydrous sodium sulfate was added to the product to remove water from the solution, and chlorobenzene was used as an internal standard, and the yield of the target product furfural amine was determined by gas chromatography-mass spectrometry as shown in Table 1.

[0131] Table 1. Summary of reaction results of Example 24

[0132] Number of reactions Furfural conversion rate (%) Furfurylamine yield (%) 1 100 99 2 100 97 3 100 95 4 100 94 5 100 94 6 100 93 7 100 92 8 100 91 9 100 91 10 100 90

[0133] Comparative Example 1: One-step catalytic amination of furfural to prepare furfurylamine using Ru / ZrO2 catalyst

[0134] First, RuCl3·H2O and urea were dissolved in water respectively to prepare 10 mg / mL RuCl3·H2O solution and 15 mg / mL urea aqueous solution. Then, 0.6 g ZrO2 was dispersed in 40 mL water. 1.34 mL of RuCl3·H2O solution was added thereto under stirring at room temperature and stirred for 30 min. Then, 40 mL of urea aqueous solution was added and the mixture was placed in a constant temperature water bath at 80°C and stirred for 4 h. After the reaction was completed, the mixture was centrifuged, washed with deionized water, and dried. In an atmosphere of nitrogen, the temperature was increased to 500°C at a heating rate of 5°C / min, and the mixture was calcined at a constant temperature for 3 h. In an atmosphere of hydrogen, the temperature was increased to 400°C at a heating rate of 5°C / min, and the mixture was calcined at a constant temperature for 3 h to obtain the catalyst Ru / ZrO2.

[0135] The yield of furfurylamine obtained under the same feed mass and reaction conditions as in Example 2 was 2%.

[0136] Comparative Example 2: One-step catalytic amination of furfural to prepare furfurylamine using Ru / 8ZrW catalyst

[0137] During the preparation of the catalyst Ru / 8ZrW, other parts were the same as in Example 1, except that the amount of ammonium metatungstate added was 0.6 g, and the catalyst Ru / 8ZrW was prepared.

[0138] The yield of furfurylamine obtained under the same feed mass and reaction conditions as in Example 2 was 47%.

[0139] Comparative Example 3: One-step catalytic amination of furfural to prepare furfurylamine using Ru / 32ZrW catalyst

[0140] During the preparation of the catalyst Ru / 32ZrW, other parts were the same as in Example 1, except that the amount of ammonium metatungstate added was 0.15 g, and the catalyst Ru / 32ZrW was prepared.

[0141] The yield of furfurylamine obtained under the same feed mass and reaction conditions as in Example 2 was 51%.

[0142] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0143] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A method for preparing an amine compound, characterized in that: The preparation method of the amine compound comprises: reacting an aldehyde ketone substrate and ammonia water in a solvent under the conditions of a catalyst and hydrogen to generate an amine compound; wherein the catalyst comprises a zirconium-tungsten composite carrier and ruthenium loaded on the zirconium-tungsten composite carrier.

2. The method for preparing an amine compound according to claim 1, characterized in that: The aldehyde-ketone substrate has a structure shown in formula (I): The amine compound has a structure shown in formula (II): In formula (I) and formula (II), R1 and R2 are independently selected from H, or independently selected from the following substituted or unsubstituted groups: saturated heterocyclic group, unsaturated heterocyclic group, carbocyclic aromatic group, carbocyclic aromatic group C 1-10 Alkyl, unsaturated heterocyclic group C 1-10 Alkyl; the substituted substituents are selected from one or more of the following groups: C 1-10 Alkyl, hydroxyl C 1-10 Alkyl, C 1-10 Alkoxy, halogen, C 1-10 Alkoxycarbonyl, -NR a R b , Carbocyclic aromatic group, carbocyclic aromatic group C 1-10 Alkoxy, hydroxyl, R a , R b Independently selected from H, C 1-10 alkyl; R1 and R2 are not H at the same time; Alternatively, R1 and R2 are connected to form a 3-12 membered carbocyclic ring with the carbon atom to which they are connected; The saturated heterocyclic group, the unsaturated heterocyclic group, the unsaturated heterocyclic group C 1-10 The heteroatom in the alkyl group is selected from one or more of O, N and S.

3. The method for preparing an amine compound according to claim 2, characterized in that: R1 is selected from H, and R2 is selected from the following substituted or unsubstituted groups: Where X is O, NH or S, Y is CH or N, R c Selected from C 1-10 Alkyl, R d Selected from C 1-10 alkyl.

4. The method for preparing an amine compound according to claim 2, characterized in that: R2 is selected from R3 is selected from H, hydroxyl C 1-6 Alkyl or C 1-6 Alkyl, R4, R5 are independently selected from H, C 1-6 Alkyl, fluorine, chlorine, bromine, C 1-6 Alkoxy, C 1-6 Alkoxycarbonyl, -N(CH3)CH3 or R6 is selected from C 1-6 Alkyl, fluorine, chlorine, bromine or C 1-6 Alkoxy; m is 1-6, t is 1-3.

5. The method for preparing an amine compound according to claim 2, characterized in that: R2 is selected from 6. The method for preparing an amine compound according to claim 1, characterized in that: R1 and R2 are connected to form a 5-7 membered carbon ring with the carbon atom to which they are connected.

7. The method for preparing an amine compound according to claim 1, characterized in that: The reaction is carried out at 60-120°C, and further at 60-100°C; and / or, for every 1mmol of aldehyde-ketone substrate, the amount of ammonia water added is 0.5-1.5mL, and the mass concentration of ammonia water is 25%-28%; and / or, the solvent is an organic solvent, and the organic solvent includes an alcohol compound, and the alcohol compound includes isopropanol; and / or, the pressure of the hydrogen is controlled to be 0.5-1.5MPa; and / or, for every 1mmol of aldehyde-ketone substrate, the amount of the catalyst added is 25-35mg, and the amount of the solvent added is 4-6mL; and / or, in the zirconium-tungsten composite carrier, the molar ratio of the zirconium to the tungsten is 8-32:

1.

8. The method for preparing an amine compound according to claim 1, characterized in that: The catalyst is prepared by the following method: (1) dispersing ammonium metatungstate and zirconium nitrate in water, adjusting the system to be alkaline, reacting under heating conditions, separating solids, and then calcining in an air atmosphere to obtain a zirconium-tungsten composite carrier; (2) The zirconium-tungsten composite carrier and the ruthenium source are dispersed in water, urea is added, and the mixture is reacted under heating conditions. The solid is separated and then calcined in a protective atmosphere and a hydrogen atmosphere in sequence.

9. The method for preparing an amine compound according to claim 8, characterized in that: In step (1), the zirconium nitrate is used as a raw material in the form of zirconium nitrate pentahydrate; and / or, in step (1), the pH value of the system is adjusted to 9.5-10.5 by adding ammonia water; and / or, in step (1), the mass ratio of the ammonium metatungstate to the zirconium nitrate pentahydrate is 25-50:1, further 25-40:1, further 25-35:1; and / or, in step (1), the heating conditions are controlled so that the reaction temperature is 70-90°C; and / or, in step (1), the calcination temperature is 500-600°C; and / or, in step (1), the heating rate of the calcination is controlled to be 1-10°C / min, further 2-8°C / min, further 4-6°C / min; and / or, in step (1), the calcination time is controlled to be 1-10h, further 3-6h.

10. The method for preparing an amine compound according to claim 8, characterized in that: In step (2), the ruthenium source is a ruthenium halide, further, the ruthenium halide includes ruthenium trichloride, and further, the ruthenium trichloride is in the form of RuCl3·H2O as a raw material; and / or, in step (2), the mass ratio of the ruthenium source, the zirconium-tungsten composite carrier and the urea is 1:40-50:40-50; and / or, in step (2), the ruthenium source and the urea are added in the form of aqueous solutions respectively; and / or, in step (2), the heating conditions are controlled so that the reaction temperature is 70-90°C; and / or, in step (2), the protective atmosphere is a nitrogen atmosphere or an inert gas atmosphere; and / or, in step (2), the calcination under the protective atmosphere is controlled at The calcination process is carried out at 450-550°C, further, the heating rate is controlled to be 1-10°C / min, further to 2-8°C / min, and further to 4-6°C / min; and / or, in step (2), the calcination time under the protective atmosphere is controlled to be 1-6h, further to 2-4h; and / or, in step (2), the calcination under the hydrogen atmosphere is controlled to be carried out at 350-450°C, further, the heating rate is controlled to be 1-10°C / min, further to 2-8°C / min, and further to 4-6°C / min; and / or, in step (2), the calcination time under the hydrogen atmosphere is controlled to be 1-6h, further to 2-4h.

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