CN110746377A - Method for synthesizing 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis - Google Patents

Method for synthesizing 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis Download PDF

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CN110746377A
CN110746377A CN201911079298.9A CN201911079298A CN110746377A CN 110746377 A CN110746377 A CN 110746377A CN 201911079298 A CN201911079298 A CN 201911079298A CN 110746377 A CN110746377 A CN 110746377A
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substituted pyrrolidine
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piperidine
ammonia
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CN110746377B (en
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邓友全
龙焱
刘士民
卢六斤
马祥元
何昱德
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a method for synthesizing 1-substituted pyrrolidine/piperidine derivatives by supported metal catalysis, which takes supported metal as a catalyst, 1, 4-butanediol/1, 5-pentanediol as a cyclization raw material, alcohol as an N-alkylation raw material, and reacts with ammonia to form pyrrolidine ring/piperidine ring, and the 1-substituted pyrrolidine/piperidine derivatives are synthesized by one-step reaction with high selectivity. The active components of the supported metal catalyst are Cu, Ni and Pd/Ru, the total load of the active components Cu and Ni is 3-15 wt% of the carrier, and the load of the Pd/Ru is 0-1 wt% of the carrier. The method is simple, low in cost and environment-friendly, the conversion rate of the 1, 4-butanediol/1, 5-pentanediol is high, the selectivity of the pyrrolidine/piperidine derivative is high, and the method is a production route with practical application value.

Description

Method for synthesizing 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis
Technical Field
The invention relates to a synthesis method of a 1-substituted pyrrolidine/piperidine derivative, in particular to a method for synthesizing the 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis, belonging to the technical field of catalysts and chemical synthesis.
Background
Pyrrolidine and piperidine derivatives are very important platform chemicals in the field of chemical industry, and can be used as medicines and organic intermediates, pesticides, special solvents, raw materials of onium ionic liquids and the like.
The traditional method for synthesizing pyrrolidine comprises 1: pyrrolidine derivative is synthesized by taking pyrrolidine as a raw material and reacting with aldehydes, alcohols and the like, such as fine and special chemicals, 2004, 24-25, formaldehyde is taken as a methylation raw material and reacts with pyrrolidine in a formic acid medium to prepare N-methylpyrrolidine, hydrochloric acid is added after the reaction is finished, and products are obtained by distillation, filtration and NaOH neutralization, a large amount of NaOH is needed for neutralization in the route, useless waste salt is generated, and the environmental pollution is serious; journal of the American Chemical Society, 137(40), 12796-. 2: the hydrogenation reduction method is characterized in that a catalyst is used for catalyzing N-alkyl pyrrolidone and pyrrole derivatives to prepare the 1-substituted pyrrolidine derivatives through hydrogenation reduction, although the reaction conditions of the route are mild, the reaction is green, and the product yield is high, the catalyst of the route is usually used for noble metals, and the price of the N-alkyl pyrrolidone and the pyrrole derivatives is high, so that the industrial application of the N-alkyl pyrrolidone and the pyrrole derivatives is limited. 3: amine alcohol dehydrocyclization methods, such as Beilstein J. org. chem. 2017.13: 329-337, report that the synthesis of pyrrolidine derivatives by amine alcohol dehydrocyclization can yield the desired product in high yield, but amine alcohol as a raw material itself is expensive, has a complex structure and increases the cost of the raw material.
A method of combining conventional 1-piperidine derivatives comprises 1: piperidine alkylation, which is similar to pyrrolidine alkylation, as in Journal of Organic Chemistry, 70(6),2195-2199, 2005, which reports the synthesis of 1-substituted piperidine derivatives from aldehydes and piperidine; catalysis Communications, 8(3), 576-582, 2007 synthesis of 1-substituted piperidine derivatives from alkyl halides and piperidine as raw materials; organic Letters, 15, (2), 266-. 2: hydrogenation reduction method: derivatives of piperidine obtained by reduction of a piperidone derivative carrying a 1-substitution are reported, for example, by Angewandte Chemie, International Edition, 52(8), 2231-2234; 2013; chinese patents CN102091638A and CN102093283A report methods for preparing 1-substituted piperidine derivatives by hydrogenation of pyridine derivatives, which have the problems of expensive raw materials and need of noble metal catalysts, although the reaction conditions are mild and the product yield is high; 3: amine alcohol dehydrative ring method, such as Catalysis Science & Technology, 4(1),47-52, 2014, reports that a series of piperidine derivatives synthesized by amine alcohol dehydrative ring can obtain high yield of target products, but amine alcohol as raw material is expensive and has complex structure, thus limiting the industrial application of the method.
The amination and cyclization synthesis of pyrrolidine and piperidine derivatives by using 1, 4-butanediol/1, 5-pentanediol and primary amine is an economic and green method, but the primary amine with longer carbon chain has high activity, and the secondary amine and tertiary amine are inevitably generated by mutual deamination easily in the reaction process, for example, the Journal of organic Chemistry 1989.373: 343-352 reports that the yield of 1-butylpyrrolidine is only 36 percent. The large amount of by-products produced lowers the yield of the desired product and also causes difficulties in separation and purification.
Disclosure of Invention
The invention aims to provide a method for synthesizing 1-substituted pyrrolidine/piperidine derivatives by supported metal catalysis.
The invention relates to a method for catalytically synthesizing 1-substituted pyrrolidine/piperidine derivatives, which takes supported metal as a catalyst, adopts 1, 4-butanediol/1, 5-pentanediol, ammonia and alcohol as raw materials, and adopts the method in H2Under a reducing atmosphere inAnd reacting at 230-330 ℃ under an initial pressure of 2-4 Mpa for 1-8 h to obtain the 1-substituted pyrrolidine/piperidine derivative in one step. The synthetic route is as follows:
Figure 80685DEST_PATH_IMAGE001
the raw material alcohol is C2-C8Straight chain alcohols, benzyl alcohols to benzyl alcohols with straight chain side chains.
The raw material ammonia is 20-80 wt.% ammonia water solution or ammonia gas; the molar ratio of the raw material 1, 4-butanediol/1, 5-pentanediol/ammonia/alcohol is 1:1:1 to 1:3: 3.
H2The molar ratio of the 1, 4-butanediol/1, 5-pentanediol is 0.3:1 to 0.6: 1.
The dosage of the supported metal catalyst is 5-20% of the total mass of 1, 4-butanediol/1, 5-pentanediol and alcohol.
The supported metal catalyst comprises an active component and a catalyst carrier; the catalyst comprises active components, a catalyst carrier and a catalyst carrier, wherein the active components are Cu, Ni and Pd/Ru, the total load of the active components Cu and Ni is 3-15% of the mass of the catalyst carrier, and the mass ratio of Cu to Ni is 1: 1; the total load of Pd/Ru is 0-1% of the mass of the catalyst carrier. The catalyst carrier is Al2O3、SiO2Or a ZSM-5 molecular sieve.
The preparation of the supported metal catalyst is that the salt of Cu, Ni and Pd/Ru metal is loaded on Al by an immersion method2O3、SiO2Or ZSM-5 molecular sieve. The method specifically comprises the following steps: is prepared from Ni (NO)3)2·6H2O、Cu(NO3) ·3H2Stirring and dissolving O, ammonium chloropalladate/ruthenium trichloride hydrate in deionized water, slowly adding a catalyst carrier, fully stirring and uniformly mixing at room temperature, standing and aging for 1-3 h, and then drying in an oven at 100-110 ℃ for 10-12 h; and finally, roasting the mixture for 2 to 5 hours in a muffle furnace at the temperature of between 300 and 500 ℃ to obtain the supported metal catalyst.
Compared with the prior art, the invention has the following advantages: the method has the advantages that the supported metal is used as a catalyst, 1, 4-butanediol or 1, 5-pentanediol is used as a cyclization raw material, alcohol is used as an N-alkylation raw material and reacts with ammonia to form pyrrolidine ring/piperidine ring, and the 1-substituted pyrrolidine/piperidine derivative is synthesized in a one-step reaction high-selectivity mode, so that the reaction process is greatly simplified, the raw material cost is saved, the raw materials are cheap and easy to obtain, the method is environment-friendly, and a production route with practical application value is provided.
Detailed Description
For a better understanding of the present invention, the process of the 1-substituted pyrrolidine/piperidine derivatives of the present invention is further illustrated by the specific examples below.
Example 1: preparation of 1-butylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: 27.8g of Ni (NO) are weighed out3)2·6H2O、21.1g Cu(NO3)2·3H2Adding O and 1g of ammonium chloropalladate (containing 0.37g of Pd) into a 3L beaker, adding 56ml of deionized water, stirring and dissolving at room temperature, slowly adding 185g of ZSM-5(NKF-5-80HW) molecular sieve, placing at room temperature after charging, fully stirring, standing and aging for 3h, placing in a 110 ℃ oven for drying for 12h, placing in a muffle furnace for roasting at 500 ℃ for 3h after drying, and obtaining the 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst;
(2) preparation of 1-butylpyrrolidine: accurately weighed 360g of 1, 4-butanediol (BDO, 4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 356g of n-butanol (4.8mol), 72g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst, in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of BDO is 100 percent, and the selectivity of 1-butyl pyrrolidine is 85 percent.
Example 2: preparation of 1-ethylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-ethylpyrrolidine: accurately weigh 360g BDO (4 mol), 328g 25wt.% ammonia in water (containing 4.8mol ammonia), 220g ethanol (4.8mol), 58g 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of BDO is 100 percent, and the selectivity of 1-ethylpyrrolidine is 71 percent.
Example 3 preparation of 1-Propylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-propylpyrrolidine: accurately weigh 360g BDO (4 mol), 328g 25wt.% aqueous ammonia solution (containing 4.8mol ammonia), 288g propanol (4.8mol), 65g 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of BDO is 100 percent, and the selectivity of 1-propyl pyrrolidine is 75 percent.
Example 4: preparation of 1-pentylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-pentylpyrrolidine: accurately weighed 360g of BDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 424g of n-pentanol (4.8mol), 78g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst, in a 4L reactor at 4MPaH2And (2) reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of BDO is 100 percent, and the selectivity of 1-pentyl pyrrolidine is 73 percent.
Example 5: preparation of 1-hexylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-hexylpyrrolidine: accurately weighed 360g BDO (4 mol), 328g 25wt.% aqueous ammonia solution (containing 4.8mol ammonia), 488g n-hexanol (4.8mol), 85g 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst, in a 4L reactor at 4MPaH2Reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of BDO is 100 percent, and the selectivity of 1-hexylpyrrolidine is 71 percent.
Example 6: preparation of 1-ethylpiperidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-ethylpiperidine: exactly 416 g of 1, 5-pentanediol (PDO, 4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 220g of ethanol (4.8mol), 63g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2And (2) reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of PDO is 100%, and the selectivity of 1-ethyl piperidine is 78%.
Example 7: preparation of 1-propylpiperidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-propylpiperidine: accurately weigh 416 g of PDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 288g of propanol (4.8mol), 40g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of PDO is 100 percent, and the selectivity of 1-propylpiperidine is 75 percent.
Example 8: preparation of 1-butylpiperidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-butylpiperidine: accurately weighed 416 g of PDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 356g of n-butanol (4.8mol), 77g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2And (2) reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of PDO is 100%, and the selectivity of 1-butyl piperidine is 74%.
Example 9: preparation of 1-pentylpiperidines
(2) Preparation of 1-pentylpiperidine: accurately weighed 416 g of PDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia)), 424g of n-pentanol (4.8mol), 84g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst, in a 4L reactor at 4MPaH2And (2) reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4h, wherein the conversion rate of PDO is 100% and the selectivity of 1-pentylpiperidine is 77%.
Example 10: preparation of 1-hexylpiperidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-hexylpiperidine: accurately weighed 416 g of PDO (4 mol), 328g of a 25wt.% aqueous ammonia solution ((II))4.8mol ammonia), 488g of n-hexanol (4.8mol), 90g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPaH2Reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of PDO is 100 percent, and the selectivity of 1-hexylpiperidine is 71 percent.
Example 11: preparation of 1-butylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Ru/ZSM-5: weighing 27.8g of Ni (NO3) 2.6H 2O, 21.1g of Cu (NO3), 3H2O and 1g of ruthenium trichloride hydrate (containing Ru 0.375 g) and adding the mixture into a 3L beaker, adding 56ml of deionized water, stirring and dissolving the mixture at room temperature, slowly adding 185g of ZSM-5(NKF-5-80HW) molecular sieve, fully stirring the mixture at room temperature after the materials are added, standing and aging the mixture for 3 hours, and drying the mixture in a 110 ℃ oven for 12 hours; after drying, placing the mixture in a muffle furnace for roasting at 500 ℃ for 3h to obtain a catalyst 3% of Cu, 3% of Ni and 0.2% of Ru/ZSM-5;
(2) preparation of 1-butylpyrrolidine: accurately weighed 360g BDO (4 mol), 328g 25wt.% aqueous ammonia solution (containing 4.8mol ammonia), 356g n-butanol (4.8mol), 72g 3% Cu-3% Ni-0.2% Ru/ZSM-5 catalyst, in a 4L reactor at 4MPa H2And (2) reacting under an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of BDO is 100 percent, and the selectivity of 1-butyl pyrrolidine is 79 percent.
Example 12: preparation of 1-benzylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-benzylpyrrolidine: accurately weighed accurately 360g BDO (4 mol), 328g 25wt.% aqueous ammonia solution (containing 4.8mol ammonia), 520g benzyl alcohol (4.8mol), 94g 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of BDO is 100 percent, and the selectivity of 1-benzylpyrrolidine is 28 percent.
Example 13: preparation of 1-benzylpiperidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-benzylpiperidine: quasi-drugA weight of 416 g PDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol ammonia), 520g benzyl alcohol (4.8mol), 94g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst was determined in a 4L reactor at 4MPaH2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of PDO is 100 percent, and the selectivity of 1-benzyl piperidine is 37 percent.
Example 14: preparation of 1-butylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) preparation of 1-butylpyrrolidine: accurately weighed 360g of BDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 356g of n-butanol (4.8mol), 72g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst in a 4L reactor at 2MPa H2And (2) reacting in an atmosphere, setting the reaction temperature to 290 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of BDO is 100 percent, and the selectivity of 1-butyl pyrrolidine is 74 percent.
Example 15: preparation of 1-butylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni/ZSM-5: 27.8g of Ni (NO) are weighed out3)2·6H2O、21.1g Cu(NO3)·3H2Adding O, adding into a 3L beaker, adding 56ml of deionized water, stirring and dissolving at room temperature, slowly adding 185g of ZSM-5 molecular sieve, fully stirring at room temperature after the feeding is finished, standing and aging for 3h, and drying in an oven at 110 ℃ for 12 h; after drying, placing the mixture in a muffle furnace for roasting for 3 hours at 500 ℃ to obtain a catalyst 3% Cu-3% Ni/ZSM-5;
(2) preparation of 1-butylpyrrolidine: accurately weighed 360g of BDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 356g of n-butanol (4.8mol), 71.6g of 3% Cu-3% Ni/ZSM-5 catalyst, in a 4L reactor at 4MPa H2The reaction is carried out under the atmosphere, the reaction temperature is set to 290 ℃, the reaction is finished after 4 hours of reaction, the conversion rate of BDO is 100 percent, and the selectivity of 1-butyl pyrrolidine is 54 percent.
Example 16: preparation of 1-butylpyrrolidine
(1) Preparation of catalyst 3% Cu-3% Ni-0.2% Pd/ZSM-5: the same as example 1;
(2) 1-butylpyrrolidineThe preparation of (1): accurately weighed 360g of BDO (4 mol), 328g of a 25wt.% aqueous ammonia solution (containing 4.8mol of ammonia), 592 g of n-butanol (8 mol), 62g of 3% Cu-3% Ni-0.2% Pd/ZSM-5 catalyst, in a 4L reactor at 4MPa H2And (2) reacting under an atmosphere, setting the reaction temperature to be 300 ℃, and finishing the reaction after reacting for 4 hours, wherein the conversion rate of BDO is 100 percent, and the selectivity of 1-butyl pyrrolidine is 84 percent.
In the above examples, the conversion of 1, 4-butanediol/1, 5-pentanediol and the selectivity of 1-substituted pyrrolidine/piperidine derivatives were analyzed under test conditions: and adding an internal standard substance biphenyl into a product obtained after the reaction, and carrying out quantitative analysis by an internal standard method and adopting an Agilent Technologies 7890A gas chromatography system for quantitative analysis. The chromatographic conditions are as follows: chromatography column 30 m × 0.25mm × 0.33 μm capillary, hydrogen Flame Ionization (FID) detector. Qualitative analysis was performed using Agilent technologies 7890B-5977A GC-MS under the following chromatographic conditions: a 30 m x 0.25mm x 0.25 μm capillary tube of a chromatographic column, an EI ion source, a long-acting high-energy electron multiplier detector.

Claims (8)

1. A process for synthesizing 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis includes such steps as using the supported metal as catalyst, 1, 4-butanediol/1, 5-pentanediol, ammonia and alcohol as raw materials, and reacting in H2And reacting for 1-8 h at 230-330 ℃ and initial pressure of 2-4 Mpa in a reducing atmosphere to obtain the 1-substituted pyrrolidine/piperidine derivative in one step.
2. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 1, wherein: the raw material alcohol is C2-C8Straight chain alcohols, benzyl alcohols to benzyl alcohols with straight chain side chains.
3. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 1, wherein: the raw material ammonia is 20-80 wt.% ammonia water solution or ammonia gas.
4. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 1, wherein: the molar ratio of the raw material 1, 4-butanediol/1, 5-pentanediol/ammonia/alcohol is 1:1:1 to 1:3: 3.
5. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 1, wherein: h2The molar ratio of the 1, 4-butanediol/1, 5-pentanediol is 0.3:1 to 0.6: 1.
6. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 1, wherein: the dosage of the supported metal catalyst is 5-20% of the total mass of 1, 4-butanediol/1, 5-pentanediol and alcohol.
7. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to any one of claims 1 to 6, wherein: the supported metal catalyst comprises an active component and a catalyst carrier, wherein the active component is Cu, Ni and Pd/Ru, the total load capacity of the active component Cu and Ni is 3-15% of the mass of the catalyst carrier, and the mass ratio of Cu to Ni is 1: 1; the total load capacity of Pd/Ru is 0-1% of the mass of the catalyst carrier; the catalyst carrier is Al2O3、SiO2Or a ZSM-5 molecular sieve.
8. The process for the catalytic synthesis of 1-substituted pyrrolidine/piperidine derivatives according to claim 7, wherein: the supported metal catalyst is prepared by mixing Ni (NO)3)2·6H2O、Cu(NO3) ·3H2Stirring and dissolving O, ammonium chloropalladate/ruthenium trichloride hydrate in deionized water, slowly adding a catalyst carrier, fully stirring and uniformly mixing at room temperature, standing and aging for 1-3 h, and then drying in an oven at 100-110 ℃ for 10-12 h; and finally, roasting the mixture for 2 to 5 hours in a muffle furnace at the temperature of between 300 and 500 ℃ to obtain the supported metal catalyst.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900832A (en) * 1988-08-02 1990-02-13 Air Products And Chemicals, Inc. Process for the catalytic animation of alcohols and diols using non-acidic hydroxyapatite catalysts
US20020183517A1 (en) * 2001-03-27 2002-12-05 Council Of Scientific & Industrial Research Process for the synthesis of an aliphatic cyclic amine
JP2007197422A (en) * 2005-12-28 2007-08-09 Kao Corp Method for producing nitrogen-containing compound
CN101508683A (en) * 2009-03-30 2009-08-19 刘丽川 Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol
CN102091638A (en) * 2009-12-10 2011-06-15 中国科学院大连化学物理研究所 Catalyst for use in preparation of piperidine and piperidine derivatives
CN104470907A (en) * 2012-07-13 2015-03-25 巴斯夫欧洲公司 Method for producing pyrollidine
CN110038576A (en) * 2019-05-05 2019-07-23 中国科学院兰州化学物理研究所 A kind of load type metal catalyst and its preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900832A (en) * 1988-08-02 1990-02-13 Air Products And Chemicals, Inc. Process for the catalytic animation of alcohols and diols using non-acidic hydroxyapatite catalysts
US20020183517A1 (en) * 2001-03-27 2002-12-05 Council Of Scientific & Industrial Research Process for the synthesis of an aliphatic cyclic amine
JP2007197422A (en) * 2005-12-28 2007-08-09 Kao Corp Method for producing nitrogen-containing compound
CN101508683A (en) * 2009-03-30 2009-08-19 刘丽川 Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol
CN102091638A (en) * 2009-12-10 2011-06-15 中国科学院大连化学物理研究所 Catalyst for use in preparation of piperidine and piperidine derivatives
CN104470907A (en) * 2012-07-13 2015-03-25 巴斯夫欧洲公司 Method for producing pyrollidine
CN110038576A (en) * 2019-05-05 2019-07-23 中国科学院兰州化学物理研究所 A kind of load type metal catalyst and its preparation method and application

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
G. BITSI 等: "N-alkylation d’amines en catalyse homogène. Synthèse de mono- et de diamines cycliques", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *
R. GRIGG 等: "Transition metal-catalysed N-alkylation of amines by alcohols", 《 J. CHEM. SOC., CHEM. COMMUN.》 *
XINJIANG CUI 等: "Development of a General Non-Noble Metal Catalyst for the Benign Amination of Alcohols with Amines and Ammonia", 《CHEM. EUR. J.》 *
YAN LONG 等: "One-pot synthesis of N-methylpyrrolidine (NMPD) using Cu- and Ni-modified ZSM-5 as an efficient catalyst", 《GREEN CHEM.》 *
温晓燕: "气相催化合成四氢吡咯的研究进展", 《应用化工》 *

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