CN111087309B - Method for preparing 2-methylbutylamine by one-step method - Google Patents
Method for preparing 2-methylbutylamine by one-step method Download PDFInfo
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- CN111087309B CN111087309B CN201911317143.4A CN201911317143A CN111087309B CN 111087309 B CN111087309 B CN 111087309B CN 201911317143 A CN201911317143 A CN 201911317143A CN 111087309 B CN111087309 B CN 111087309B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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 method for preparing 2-methylbutylamine by a one-step method, which aims to solve the problems of low reaction yield and difficult obtainment of raw materials in the prior art. The method takes L-isoleucine as a raw material, and hydrogenation reduction decarboxylation is carried out under the high-pressure heating condition. The present invention is through the use of a highly selective amino acid decarboxylation catalyst. The selectivity can be stabilized at more than 90 percent, and the method has good industrial application value. The conversion rate and the selectivity of the 2-methylbutylamine are high and can reach more than 90 percent.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthetic route for preparing 2-methylbutylamine by decarboxylation of isoleucine by using a catalyst.
Background
The preparation of 2-methylbutylamine by decarboxylation of isoleucine is an ideal synthetic route, theoretically, only CO is available 2 A by-product. However, the preparation of chemicals by catalytic conversion using amino acids as raw materials faces many challenges, and the amino acids have a plurality of functional groups, i.e. a special structure of an amino group and a carboxyl group, so that the amino acids generate different products under different reaction conditions.
The current common route for preparing 2-methylbutylamine is that 2-methyl isobutyl alcohol is used as a raw material catalyst to catalyze and complete the conversion under high-pressure reaction conditions according to literature reports, and the yield is 65% (Angewandte Chemie, international edition,47 (45), 8661-8664. 2-methylbutanone as a raw material can also be converted into 2-methylbutylamine under alkaline conditions (PCT int.appl.,2019008110, 10Jan2019).
Disclosure of Invention
The invention aims to solve the technical problems of low yield, complex technical process and the like in the process of preparing 2-methylbutylamine in the prior art, and provides a method for preparing 2-methylbutylamine with high conversion rate and high selectivity.
The invention uses cheap and easily obtained L-isoleucine as raw material, uses the amino acid decarboxylation catalyst, and carries out the reaction of one-step method in a pressure vessel. The method for preparing the 2-methylbutylamine by the one-step method specifically comprises the following steps:
(1) Dissolving L-isoleucine in deionized water, adding the deionized water into a reaction kettle with a polytetrafluoroethylene lining, adding a proper amount of an amino acid decarboxylation catalyst, sealing the reaction kettle, detecting leakage, and replacing air in the kettle with nitrogen for more than 6 times;
(2) Slowly introducing hydrogen to reach the initial set pressure, and controlling the pressure range to be 2-10 MPa;
(3) After leakage detection is finished, stirring and heating are started, the rotating speed of a stirring paddle is 200-400rpm, and the heating rate is 6 ℃/min;
(4) Heating to a set temperature, keeping for 2-6 h, and keeping stirring;
(5) Stopping heating and keeping stirring after the set reaction time is reached, and naturally cooling to room temperature;
(6) Slowly decompressing, filtering the catalyst to obtain the 2-methylbutylamine aqueous solution.
The amino acid decarboxylation catalyst used in the invention is prepared by loading a precursor on nano TiO by using an impregnation method 2 The precursor is ruthenium metal salt, the mass percentage of the precursor is 0.1-10%, and the balance is TiO 2 (ii) a The nano TiO is 2 The grain diameter is 10-50 nm; the ruthenium metal salt is one of ruthenium chloride, ruthenium ammonia complex or chlorine ruthenate complex salt; the TiO is 2 Is Ti with high specific surface area prepared by adopting a low-temperature liquid phase method 3+ The anatase phase carrier with a defect structure has a spherical geometric structure or a multi-level hole structure.
The preparation method specifically comprises the following steps:
(1) Adding TiOSO into nitric acid water solution 4 Ultrasonic dissolving to form transparent solution;
(2) Stirring the transparent solution obtained in the step (1), adding a polyethylene glycol-2000 dispersing agent, continuously stirring for 1h, and carrying out water bath at the temperature of 50-90 ℃ for 2-6 h to obtain a suspension;
(3) Centrifuging and filtering the suspension obtained in the step (2), washing with water and alcohol for 3 times respectively, drying at 50 ℃ for 12h, and roasting at 350-450 ℃ in air atmosphere for 4h to obtain anatase type nano TiO with high specific surface area 2 ；
(4) Adding ruthenium metal salt into deionized water or absolute ethyl alcohol, dispersing for 1-4 h by using ultrasonic, and then adding the nano TiO prepared in the step (3) 2 Stirring for 6-24 h to obtain a material;
(5) Centrifuging, washing and drying the material obtained in the step (4), and roasting for 4-8 h at 250-650 ℃ in an air atmosphere; is arranged at H 2 Atmosphere, 100 ℃EReducing at 650 ℃, granulating, molding and drying to obtain the amino acid decarboxylation catalyst.
The invention has the beneficial effects that:
(1) Compared with the background literature, the conversion rate and the selectivity of the 2-methylbutylamine are higher and can reach more than 90 percent.
(2) Compared with the background literature, the synthetic steps of the 2-methylbutylamine are simple.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
The catalyst evaluation was carried out using an autoclave reactor equipped with a polytetrafluoroethylene liner and a stirring paddle. The reaction was carried out at high temperature and high pressure with the catalyst accounting for 5wt% of the reaction substrate. After the reaction kettle is sealed, N is firstly used 2 The air in the autoclave was replaced 6 times and pressurized to a specific initial pressure by introducing hydrogen. The stirring was turned on and the temperature was started. Keeping the temperature at 180 ℃ for reaction for 4-8 h, stopping heating and naturally cooling, and sampling and analyzing.
The analytical instruments are Shimadzu GC-2014 gas chromatography, hydrogen flame ion detector and DB-1701 chromatographic column. The selectivity and conversion were calculated according to the formula.
Example 1
A2% dilute nitric acid solution containing 100mL was placed in a 50 ℃ water bath. While stirring, 8g of TiOSO was added 4 Wherein TiOSO 4 The volume ratio to the aqueous nitric acid solution was 1. While maintaining stirring, 6mL of polyethylene glycol-2000 was added dropwise. The resulting mixture was stirred at 50 ℃ for 6h, and the suspension was centrifuged and filtered. Then washing with water and ethanol for three times, drying at 50 deg.C for 12h, and calcining at 450 deg.C in air atmosphere for 4h to obtain 3.52g of the prepared TiO 2 The target amount is obtained through multiple accumulation.
1.3g of RuCl 3 ·3H 2 Dissolving O in 80ml absolute ethyl alcohol, ultrasonic dissolving, adding 20g TiO 2 1, soaking for 16 hours under strong stirring; removing solvent from the obtained material, drying, washing with deionized water, drying at 100 deg.C, and air dryingRoasting for 4h at 350 ℃ in the atmosphere, and cooling to room temperature in a dry environment. After granulation, molding and drying again, the sample is placed in a hydrogen atmosphere and reduced for 3 hours at 400 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 0.52g of L-isoleucine in 40ml of deionized water, ultrasonically dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 2Mpa. Heating and stirring are started, timing is started when the temperature is 150 ℃, heating is stopped after 4 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 2
TiO 2 -1 preparation same as example 1. 3.6g of RuCl 3 ·3H 2 Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of TiO 2 -1, soaking for 24h with vigorous stirring; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, granulating, molding, drying again, roasting at 450 ℃ for 8h in an air atmosphere, and cooling to room temperature in a dry environment. And then placing the sample in a hydrogen atmosphere, and reducing for 3h at 500 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 0.26g of L-isoleucine in 40ml of deionized water, ultrasonically dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 4Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 2 hours, and the mixture is naturally cooled to room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 3
TiO 2 -1 preparation same as example 1. 3.9g of RuCl 3 ·3H 2 Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of commercially available anatase TiO 2 Strongly stirring and soaking for 24 hours; removing solvent from the obtained material, drying, washing with deionized water, oven drying at 100 deg.C, granulating, molding, and making into granuleAfter drying again, the mixture was baked at 350 ℃ for 8 hours in an air atmosphere, and cooled to room temperature in a dry environment. And then placing the sample in a hydrogen atmosphere, and reducing for 3h at 500 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 0.26g of L-isoleucine in 40ml of deionized water, ultrasonically dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 8Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 4 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 4
TiO 2 -1 preparation same as example 1. 0.6g of RuCl 3 ·3H 2 Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of commercially available anatase TiO 2 Strongly stirring and soaking for 24 hours; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, granulating, molding, drying again, roasting at 350 ℃ for 8 hours in an air atmosphere, and cooling to room temperature in a dry environment. Then placing the sample in a hydrogen atmosphere, and reducing for 3h at 500 ℃ to obtain an amino acid decarboxylation catalyst;
dissolving 0.26g of L-isoleucine in 40ml of deionized water, carrying out ultrasonic dissolution, then adding 0.24g of an amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 2Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 8 hours, and the mixture is naturally cooled to room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
The performance evaluation of the catalyst for decarboxylation of isoleucine to 2-methylbutylamine of the invention:
the reaction products obtained in examples 1 to 4 were characterized, respectively, and the results are shown in the following table.
TABLE 1 results of the reaction
| Examples | Conversion rate/% | Selectivity/%) |
| 1 | 99.9 | 92.6 |
| 2 | 98.7 | 90.3 |
| 3 | 99.9 | 95.2 |
| 4 | 97.9 | 93.5 |
And (4) conclusion: the process route for decarboxylating L-isoleucine to prepare amine is simple, the selectivity of the 2-methylbutylamine is high, the reaction can be carried out for 4 hours under the reaction conditions of 4Mpa and 150 ℃, the conversion rate is kept at 99.9%, and the selectivity is kept at over 90%.
Claims (2)
1. The one-step method for preparing 2-methylbutylamine is characterized by comprising the following steps:
(1) Dissolving L-isoleucine in deionized water, adding into a reaction kettle with a polytetrafluoroethylene lining, adding a proper amount of an amino acid decarboxylation catalyst, sealing the reaction kettle, detecting leakage, and replacing air in the kettle with nitrogen for more than 6 times;
(2) Slowly introducing hydrogen to reach the initial set pressure, wherein the pressure range is controlled to be 2 to 10Mpa;
(3) After leakage detection is finished, stirring and heating are started, the rotating speed of a stirring paddle is 200-400rpm, and the heating rate is 6 ℃/min
(4) Heating to a set temperature, keeping for 2-6 h, and keeping stirring;
(5) Stopping heating and keeping stirring after the set reaction time is reached, and naturally cooling to room temperature;
(6) Slowly decompressing, filtering the catalyst to obtain 2-methylbutylamine aqueous solution;
the preparation steps of the amino acid decarboxylation catalyst are as follows:
a. adding TiOSO into nitric acid water solution 4 Ultrasonic dissolving to form transparent solution;
b. b, keeping stirring the transparent solution obtained in the step a, adding a polyethylene glycol-2000 dispersing agent, continuing stirring for 1h, and keeping in a water bath at 50-90 ℃ for 2-6 h to obtain a suspension;
c. centrifuging and filtering the suspension obtained in the step b, washing with water and alcohol for 3 times respectively, drying at 50 ℃ for 12h, and then roasting at 350-450 ℃ for 4h in an air atmosphere to obtain anatase type nano TiO with high specific surface area 2 ；
d. Adding ruthenium metal salt into deionized water or absolute ethyl alcohol, dispersing for 1 to 4 hours by using ultrasonic, and then adding the nano TiO prepared in the step c 2 Stirring for 6 to 24 hours to obtain a material;
e. d, centrifuging, washing and drying the material obtained in the step d, and roasting for 4 to 8 hours at 250 to 650 ℃ in an air atmosphere; is arranged at H 2 Reducing at 100-650 ℃ in the atmosphere, and then granulating, molding and drying to obtain the amino acid decarboxylation catalyst.
2. The one-step method for preparing 2-methylbutylamine according to claim 1, characterized in that the amino acid decarboxylation catalyst in step (1) is prepared by loading the precursor on nano TiO by impregnation method 2 The precursor is ruthenium metal salt with mass percentThe composition is 0.1 to 10 percent, and the balance is TiO 2 (ii) a The nano TiO is 2 The particle size is 10 to 50nm; the ruthenium metal salt is one of ruthenium chloride, ruthenium ammonia complex or chlorine ruthenate complex salt; the TiO is 2 Is Ti with high specific surface area prepared by adopting a low-temperature liquid phase method 3+ The anatase phase carrier with a defect structure has a spherical geometric structure or a multi-level hole structure.
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Citations (6)
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| GB818434A (en) * | 1957-04-24 | 1959-08-19 | Monsanto Chemicals | The decarboxylation of aromatic hydroxy acids |
| CN101205160A (en) * | 2006-12-20 | 2008-06-25 | 德古萨有限责任公司 | Continuous method for decarboxylation of carboxylic acid |
| CN101578256A (en) * | 2007-01-11 | 2009-11-11 | 三菱化学株式会社 | Cadaverine salt, aqueous cadaverine salt solution, polyamide resin, molded article and process for producing cadaverine salt and aqueous cadaverine salt solution |
| WO2010002000A1 (en) * | 2008-07-03 | 2010-01-07 | 三菱化学株式会社 | Process for production of pentamethylenediamine, and process for production of polyamide resin |
| JP2014152158A (en) * | 2013-02-13 | 2014-08-25 | Ube Ind Ltd | Method of producing amine compound |
| CN110204424A (en) * | 2019-06-27 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of preparation method of biology base 2 phenylethyl alcohol |
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2019
- 2019-12-19 CN CN201911317143.4A patent/CN111087309B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB818434A (en) * | 1957-04-24 | 1959-08-19 | Monsanto Chemicals | The decarboxylation of aromatic hydroxy acids |
| CN101205160A (en) * | 2006-12-20 | 2008-06-25 | 德古萨有限责任公司 | Continuous method for decarboxylation of carboxylic acid |
| CN101578256A (en) * | 2007-01-11 | 2009-11-11 | 三菱化学株式会社 | Cadaverine salt, aqueous cadaverine salt solution, polyamide resin, molded article and process for producing cadaverine salt and aqueous cadaverine salt solution |
| WO2010002000A1 (en) * | 2008-07-03 | 2010-01-07 | 三菱化学株式会社 | Process for production of pentamethylenediamine, and process for production of polyamide resin |
| JP2014152158A (en) * | 2013-02-13 | 2014-08-25 | Ube Ind Ltd | Method of producing amine compound |
| CN110204424A (en) * | 2019-06-27 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of preparation method of biology base 2 phenylethyl alcohol |
Non-Patent Citations (2)
| Title |
|---|
| Ru-Catalyzed Hydrogenation−Decarbonylation of Amino Acids to Bio-based Primary Amines;Jasper Verduyckt等;《ACS Sustainable Chem. Eng.》;20170220;第5卷;第3292页 Scheme 1，第3293页 Table 1，第S2页1.2 * |
| Selective synthesis of primary amines directly from alcohols and ammonia;Chidambaram Gunanathan等;《Angew. Chem. Int. Ed.》;20081008;第47卷;第8661-8664页 * |
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