WO2002040442A1 - Procede d'introduction un groupe amino et procede de synthese d'acide amine - Google Patents
Procede d'introduction un groupe amino et procede de synthese d'acide amine Download PDFInfo
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- WO2002040442A1 WO2002040442A1 PCT/JP2001/009499 JP0109499W WO0240442A1 WO 2002040442 A1 WO2002040442 A1 WO 2002040442A1 JP 0109499 W JP0109499 W JP 0109499W WO 0240442 A1 WO0240442 A1 WO 0240442A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Definitions
- the present invention relates to a method for introducing an amino group into an organic acid under high temperature and high pressure, and more particularly, to an organic acid obtained by reacting an organic acid with ammonia or an ammonium salt compound under high temperature and high pressure water conditions.
- the present invention relates to a method for introducing an amino group into a compound, a method for synthesizing an amino acid from an organic acid by the above method, and a method for producing an amino acid from an organic acid.
- the present invention uses an organic acid and ammonia or an ammonium salt compound as a reaction substrate to synthesize or produce an amino acid in a batchwise manner or continuously at high temperature and high pressure without involving an organic solvent or a catalyst in the synthesis process. It provides a method that is suitable and useful as industrial technology. Background art
- amino acids are generally produced by various production means such as a fermentation method, a hydrolysis method, and an organic synthesis method.
- a fermentation method for example, for the synthesis of alanine, a microorganism fermentation method, It has been produced by a method using the hydrolyzate or an organic synthetic method using an organic reagent.
- Representative examples of conventional methods for synthesizing alanine are shown below.
- the present invention provides a method for introducing an amino group under high-temperature high-pressure water, a method for synthesizing an amino acid, and a method for producing an amino acid.
- the present invention provides an amino group-introducing method, which comprises introducing an amino group into an organic acid by reacting the organic acid with ammonia under high-temperature and high-pressure water conditions.
- a method of synthesizing an amino acid by introducing an amino group into an organic acid to synthesize an amino acid reacting an organic acid with ammonia under high-temperature and high-pressure water conditions to synthesize an amino acid by introducing an amino group into the organic acid. And then separating and purifying with an ion exchange resin. Disclosure of the invention
- an object of the present invention is to provide a novel amino group introduction method for introducing an amino group by reacting an organic acid with ammonia or an ammonium salt compound under high temperature and high pressure water conditions.
- Another object of the present invention is to provide a novel amino acid synthesis method for synthesizing an amino acid from an organic acid and ammonia or an ammonium salt compound by the above amino group introduction method.
- the present invention provides a method for introducing an amino group according to the present invention, which comprises, for example, alanine from lactic acid and ammonia or ammonium salt of hydroxy acid type, glycine from dalicholate, aspartic acid from malic acid, or tartaric acid. It is an object of the present invention to provide a novel amino acid synthesis method for synthesizing an amino acid from an organic acid, such as synthesizing 3-diaminosuccinic acid.
- the present invention introduces an organic acid and ammonia or an ammonium salt compound into a reactor under high-temperature and high-pressure water conditions, and performs a batch-type amino acid synthesis It is an object of the present invention to provide a synthesis method or a continuous amino acid synthesis method for continuously synthesizing amino acids.
- an amino acid is synthesized from an organic acid and ammonia or an ammonium salt compound by the above-described amino group introduction method, and the amino acid is separated from the obtained reaction solution using an amino acid separating material such as an ion exchange resin. It is an object of the present invention to provide a method for producing a high-purity amino acid characterized by separation and purification.
- the present invention for solving the above problems is constituted by the following technical means.
- a method for introducing an amino group which comprises introducing an amino group into an organic acid by reacting the organic acid with ammonia or an ammonium salt compound under high-temperature and high-pressure water conditions.
- a method for synthesizing an amino acid comprising reacting an organic acid with ammonia or an ammonium salt under high-temperature and high-pressure water conditions, and synthesizing an amino acid by introducing an amino group into the organic acid.
- a method for producing an amino acid characterized in that the obtained reaction solution is separated and purified using an amino acid separating material such as an ion exchange resin to obtain an amino acid.
- the corresponding hydroxy acids are reacted with ammonium and ammonium salt compounds at high temperature and high pressure to give, for example, amino acids alanine, glycine, aspartic acid or ⁇ , ⁇ -diaminosuccinic acid.
- ammonium and ammonium salt compounds at high temperature and high pressure to give, for example, amino acids alanine, glycine, aspartic acid or ⁇ , ⁇ -diaminosuccinic acid.
- lactic acid and ammonia aqueous solution ammonium acetate aqueous solution or ammonium carbonate aqueous solution are introduced into a reactor under high temperature and high pressure water conditions. Then, a method of synthesizing alanine by passing at a high speed is exemplified.
- raw material reagents used in the synthesis method of the present invention only organic acids and ammonia or ammonium salt compounds are used.
- high-temperature high-pressure water is used. Used as a reaction field or reaction solvent, no organic solvent or catalyst is used, and no particular use is required.
- the waste solvent and the waste catalyst that must be treated and the waste that requires some kind of treatment will not be discharged. Unreacted organic acid and water used can be reused in the reaction of the present invention.
- the method of the present invention is considered to be the most suitable method as a means for producing such amino acids and the like, since useful products such as amino acids can be continuously synthesized at high speed. This reaction can be carried out in a batch reactor.
- an amino acid can be synthesized by reacting ⁇ -hydroxy acid with ammonia or an ammonium salt compound under high-temperature and high-pressure water conditions, and introducing an amino group into ⁇ -hydroxy acid.
- amino acids are mainly synthesized in living organisms, but can also be synthesized organically.
- the amino acids mentioned here can be synthesized, for example, by reacting ⁇ -alanine ( ⁇ -alanine) with / 3-propiolactone (/ 3-propion 1 actone) with ammonia in an acetonitrile solvent.
- amino acid synthesis As specific examples of the amino acid synthesis according to the present invention, the respective synthetic reaction formulas of alanine, glycine, aspartic acid and arsenic ⁇ -diaminosuccinic acid are shown below.
- the temperature of the high-temperature and high-pressure water can be controlled from outside the reactor by using a heater, molten salt, or the like, or can be controlled by an internal heat method in the reactor. is there.
- high-temperature and high-pressure water can be produced in advance and injected into the reactor from outside to cause a reaction.
- the pressure in the reaction vessel can be controlled by a pressure regulating valve if it is a flow type.
- the autogenous pressure at the operating temperature can be calculated.
- the pressure can be controlled by injecting another gas such as nitrogen gas.
- the pressure used should be higher than the autogenous pressure at the operating temperature.
- high-temperature and high-pressure water with a temperature of 250 or more and a pressure of 20 MPa or more The present invention can be achieved under such conditions, but the present invention can be more suitably achieved under high-temperature and high-pressure water conditions of a temperature of 300 or more and a pressure of 25 MPa or more. Furthermore, the present invention is most preferably achieved by selecting high-temperature and high-pressure water conditions in a temperature range of 300 to 420 and a pressure range of 25 MPa to 5 OMPa. The optimal temperature conditions will vary with the treatment time, but in general, a temperature range of 250 to 450 can be preferably selected. Further, appropriate temperature and pressure conditions may be employed depending on the throughput and the reaction apparatus.
- the reactor for example, a high-temperature and high-pressure reactor is used.
- the type of the reactor is not limited as long as it can set a reaction system under high-temperature and high-pressure water conditions.
- suitable reactors include the flow-type high-temperature and high-pressure reactor and the batch-type reactor used in the present invention.
- Commercially available autoclaves are preferably used. .
- the reaction conditions vary depending on the type and concentration of the organic acid used, the types and concentrations of ammonia and ammonium salt compounds, the reaction time, and the conditions of high temperature and high pressure water.
- the organic acid used as a reaction substrate includes, for example, lactic acid, glycolic acid, malic acid, tartaric acid, hydroxy-n-butyric acid, mandelic acid, 2-hydroxy-3-methylbutyric acid, citric acid, glyceric acid And hydroxy acids having one or more hydroxyl groups and one or more hydroxyl groups in one molecule, such as tropic acid, benzylic acid, and hydroxyvaleric acid.
- hydroxy acid any of ⁇ -hydroxy acid, / 3-hydroxy acid, ⁇ -hydroxy acid, ⁇ -hydroxy acid, ⁇ -hydroxy acid, etc. can be suitably used for the reaction.
- the organic acid used for the reaction is not limited to one type, and the reaction suitably proceeds even when a mixture of two or more types is used.
- aliphatic saturated hydroxy carboxylic acids aliphatic unsaturated hydroxy carboxylic acids
- Organic acids such as hydroxycarboxylic acid such as boric acid and aromatic hydroxycarboxylic acid, and steroids are also suitably used as the reaction substrate of the present invention.
- metal salts of the above organic acids can also be used as a raw material of the present invention.
- organic acid salts such as sodium, potassium, magnesium, calcium, and ammonium are preferably used.
- the concentration of the organic acid introduced into the reactor can be controlled by controlling the flow rate of the high-temperature and high-pressure water used as the carrier water and the flow rate of the organic acid as the reaction substrate.
- the organic acid, ammonia or ammonium salt compound may be simultaneously or separately dissolved in carrier water and then subjected to the reaction.
- the concentration of the organic acid to be introduced into the reactor can be selected in the range of 1 mM to 10M.
- an appropriate concentration value between 2 mM and 5 M can be selected, and most preferably, an appropriate concentration value between 4 mM and 2 M is selected. It is not limited to these density values.
- the concentration of the charged organic acid may be simply controlled.
- the concentration of the organic acid in the reactor changes depending on the density of the high-temperature and high-pressure water involved in the reaction.
- the amount of amino group introduced and the amount of amino group introduced are controlled by adjusting the temperature, pressure, reaction time, concentration of the reaction substrate and concentration of ammonia and ammonium salt in the reaction system according to the type of the organic acid.
- the position, species of amino acid produced, amount produced or reaction yield can be manipulated.
- ammonia water or liquefied ammonia having a concentration of 28% is generally preferably used, but the reaction proceeds even if gaseous ammonia is introduced into high-temperature high-pressure water.
- ammonium salt compound ammonium acetate, ammonium carbonate, ammonium formate, ammonium chloride, ammonium sulfate and the like are preferably used.
- Ammonia and ammonium salt compounds are usually used as organic acids It is often mixed with a salt or an organic acid ester and introduced into the reactor. At that time, the ammonia and the ammonium salt compound are usually used as an aqueous solution, and when liquefied ammonia is used, it finally becomes an aqueous solution, and the reaction concentration is 1 to 1 of the organic acid salt or organic acid ester concentration. It can be selected from an appropriate value in the 0-fold concentration range. For example, the concentrations of the aqueous ammonia solution and the aqueous ammonia solution can be selected from ImM to 20 M, preferably from 2 mM to 10 M.
- an appropriate value between 4 mM and 8 M can be selected, but the present invention is not limited to these concentration values.
- the reaction of the present invention proceeds even if the organic acid and the ammonia or ammonium salt compound are separately introduced into the reactor, or if they are directly mixed with the carrier water and used. Also, the reaction of the present invention can be achieved by using a mixture of ammonia and an ammonium salt.
- the organic acid and ammonia or an ammonium salt compound of the reaction substrate may be present in high-temperature, high-pressure water at a temperature of 250 or more and a pressure of 20 MPa or more. It is not necessary to add a water-soluble catalyst such as a metal ion, an acid, or a base, a metal-supported catalyst, a solid catalyst such as a solid acid or a solid base, or an enzyme, and it is necessary to use an organic solvent. Nor.
- the present invention basically comprises reacting an organic acid with ammonia or an ammonium salt compound in the presence of the above reaction substrate in high-temperature and high-pressure water under non-catalytic conditions or without involving an organic solvent in the reaction.
- the main feature is to introduce an amino group into an organic acid and to synthesize an amino acid by using the amino acid.
- organic solvents such as methanol, ethanol, and ethylene glycol, metal ions, acids, or bases
- organic solvents such as methanol, ethanol, and ethylene glycol, metal ions, acids, or bases
- an amino group is introduced into an organic acid or an amino acid is synthesized by the above reaction system in a short period of time, for example, from about 0.01 second to about 10 minutes.
- the reaction time controls the reaction temperature, reaction pressure, high-temperature high-pressure water flow rate, reaction substrate introduction flow rate, reactor size, reactor flow path length, etc. By doing so, the reaction time can be controlled.
- the reaction time can be selected from a value in the range of 0.01 to 5 minutes, and most preferably, a value in the range of 0.05 to 2 minutes. It is not limited to a value.
- the present inventors have found that under high-temperature and high-pressure water conditions, it is possible to introduce an amino group into an organic acid in a short time (for example, a reaction time of about 0.1 second), as shown in Examples described later.
- LC-MS equipment (LC-MS equipment) ⁇ Confirmed using a FLIR-IR infrared spectrophotometer (FTIR equipment). Furthermore, by using an LC-MS apparatus, the types of organic acids and amino acids can be separated and identified, and their contents can be accurately quantified. In addition, continuously obtained amino acids are separated and purified using an ion-exchange resin, etc., and the infrared absorption spectrum is measured with an FTIR device, and compared with that of a high-grade, special-grade reagent product. It can be accurately identified. Similarly, the type and purity of the amino acid can be confirmed by NMR measurement.
- the reaction yield of the amino acid produced in the present invention varies depending on reaction conditions such as temperature and pressure, the type of organic acid, the concentration of organic acid, the concentration of ammonia and ammonium compounds, the configuration of the reaction apparatus, the size of the reactor, and the like. I do.
- the reaction yield in the case of aspartic acid synthesis using a flow-through apparatus was from 4.2% to 21.3%.
- these aspartic acids are recovered after being mixed with the raw material such as malic acid.
- various amino acids are recovered together with the raw material substrate from various organic acids or a mixture thereof.
- the obtained reaction solution is subjected to an ion exchange resin such as a cation exchange resin or an anion resin.
- amino acids and raw material substrates can be separated and purified by using an exchange resin or a combination thereof, and amino acids can be separated from each other. Therefore, amino acids can be purified and concentrated for each type.
- the raw material substrate recovered at the same time can be used again as a raw material.
- amino acids can be separated and purified by using general appropriate amino acid separation materials such as alumina, silica gel for reversed phase, zeolite, cellulose, and carbon.
- an amino acid is synthesized by reacting an organic acid with ammonia or an ammonium salt compound under high-temperature and high-pressure water conditions, and an amino acid such as an ion-exchange resin, alumina, silica gel for reversed phase, and cellulose is added to the obtained reaction solution.
- Amino acids can be separated and purified using a separating material to produce high-purity amino acids suitably.
- the presence of a predetermined concentration of an organic acid and ammonia or an ammonium salt compound as a reaction substrate in high-temperature hot water under high-temperature and high-pressure water conditions allows, for example, the production of ⁇ -hydroxy acid type lactic acid and ammonia.
- Alanine is synthesized.
- Amino groups are introduced into these organic acids by reacting nicotinic acid or tartaric acid with ammonia, and glycine, aspartic acid or ⁇ , ⁇ -diaminosuccinic acid is synthesized.
- various amino acids corresponding to the respective organic acids can be continuously synthesized.
- the present invention provides a method for introducing an amino group into an organic acid by adjusting the reaction conditions, the type of organic acid as a reaction substrate, and the concentration of an organic acid and an aqueous ammonia solution or an ammonium salt compound in the reaction system. Therefore, it is possible to synthesize an amino acid in a short time, and it is useful as a novel amino group introduction method, an amino acid synthesis method or an amino acid production method.
- Fig. 1 shows the flow sheet of a flow-type reaction device attached to two water pumps used in the present invention.
- FIG. 2 shows a flow sheet of a flow-type reaction apparatus attached to three water pumps used in the present invention.
- FIG. 3 shows an outline of a batch-type reaction tube used for the batch-type reaction and a shaking stirring-type salt bath using a mixed salt of sodium nitrate and nitrite.
- the reactor material is Alloy C one 2 7 6, the reactor internal diameter: 0. 6 5 mm and the reactor length: at 2 5 cm, therefore, the reactor volume is issued calculated as 0. 0 8 3 cm 3 Was.
- Each introduced preparation was injected with a high-pressure pump. Distilled water was used as the water used for the reaction, and Carrier water, which had been purged of dissolved oxygen by bubbling with nitrogen gas, was passed at a flow rate of 9 m1 Zmin. Using distilled water treated in the same manner, prepare a substrate solution containing 0.10 M malic acid and 0.30 M ammonia water, and react this substrate solution at a flow rate of 4.7 m1 min.
- the concentrations of each substrate before entering the reactor were malic acid: 34.3 mM and aqueous ammonia: 0.128 M.
- the reaction time was 0.240 seconds, and the aqueous solution after the reaction was examined with a high-performance liquid chromatography Ichika mass spectrometer.It was confirmed that amino groups were introduced into malic acid and aspartic acid was generated. did.
- the concentration of aspartic acid was 7.3 mM, and the reaction yield was 21.3%.
- Example 3 Under the same conditions as in Example 1, malic acid and ammonia water were continuously reacted for 1 hour.
- the resulting reaction solution was passed through a column of a cation exchange resin (50 W-X8, manufactured by Dow Chemical Company) to separate malic acid as a raw material and aspartic acid produced, and the aspartic acid-containing solution was concentrated and purified, and then purified with ethanol.
- the precipitate was collected by filtration, dried and dried to obtain 0.78 g of the product of the present invention.
- the obtained product of the present invention was in the form of a pure white powder, and it was confirmed from the results of FTIR absorption spectrum and NMR measurement that it was high-purity aspartic acid containing almost no impurities.
- Example 3 Example 3
- reaction was carried out by partially changing the reaction conditions as follows.
- the concentrations of each substrate before entering the reactor were malic acid: 19.5 mM and ammonia water: 0.0585 M.
- the reaction time was 0.22 second.When the aqueous solution after the reaction was examined with a high performance liquid chromatography mass spectrometer, it was confirmed that an amino group was introduced into the linoleic acid and aspartic acid was generated. did.
- the concentration of aspartic acid was 4.6 mM, and the reaction yield was 23.6%.
- the concentrations of the respective substrates before entering the reactor were malic acid: 47.8 mM and ammonia water: 0.144 M.
- the reaction time was 0.328 seconds.
- the concentration of aspartic acid was 5.4 mM, and the reaction yield was 11.3%. Comparative example
- the concentrations of the respective substrates before entering the reactor were malic acid: 47.8 mM and ammonia water: 0.144 M.
- the reaction time was 0.379 seconds.
- the concentrations of each substrate before entering the reactor were malic acid: 4.8 mM and aqueous ammonia: 0.0142 M.
- the reaction time was 0.064 seconds, and the aqueous solution after the reaction was examined with a high performance liquid chromatography mass spectrometer, and it was confirmed that amino groups were introduced into the malic acid and aspartic acid was generated. .
- the concentration of aspartic acid was 0.2 mM, and the reaction yield was 4.2%.
- the concentrations of the respective substrates before entering the reactor were dalicholate: 27.7 mM and ammonia water: 55.2 mM.
- the reaction time was 0.353 seconds, and the aqueous solution after the reaction was examined with a high-performance liquid chromatography mass spectrometer, and it was confirmed that an amino group was introduced into glycolic acid and glycine was generated. .
- the concentration of glycine was 1.2 mM, and the reaction yield was 4.3%.
- the concentrations of the respective substrates before entering the reactor were glycolic acid: 16.7 mM and ammonia water: 33.2 mM.
- the reaction time was 0.197 seconds, and the aqueous solution after the reaction was examined with a high-performance liquid chromatography mass spectrometer, and it was confirmed that an amino group was introduced into glycolic acid and glycine was generated. .
- the concentration of glycine was 0.7 mM, and the reaction yield was 4.2%.
- the concentrations of each substrate before entering the reactor were lactic acid: 0.310 M and aqueous ammonia: 1.429 M.
- the reaction time was 0.418 seconds, and the aqueous solution after the reaction was examined with a high performance liquid chromatography-mass spectrometer. As a result, it was confirmed that amino groups were introduced into lactic acid and alanine was generated.
- the concentration of alanine was 8.6 mM, and the reaction yield was 2.8%.
- Substrate solution flow rate 1.35 ml / min
- concentrations of the respective substrates before entering the reactor were lactic acid: 0.250 M and aqueous ammonia: 1.154 M.
- the reaction time was 0.518 seconds, and the aqueous solution after the reaction was examined with a high performance liquid chromatography-mass spectrometer. As a result, it was confirmed that an amino group was introduced into lactic acid and alanine was generated.
- the concentration of alanine was 7.7 mM, and the reaction yield was 3.1%.
- the concentrations of the respective substrates before entering the reactor were lactic acid: 0.354 M and aqueous ammonia: 1.631 M.
- the reaction time was 0.201 seconds, and the aqueous solution after the reaction was examined using a high-performance liquid chromatograph mass spectrometer.It was confirmed that amino groups were introduced into lactic acid and alanine was generated. did.
- the concentration of alanine was 7.3 mM, and the reaction yield was 2.1%.
- the concentrations of the respective substrates before entering the reactor were lactic acid: 0.249 M and aqueous ammonia: 1.150 M.
- the reaction time was 0.278 seconds, and the aqueous solution after the reaction was examined by a high performance liquid chromatography mass spectrometer. As a result, it was confirmed that an amifu group was introduced into lactic acid and alanine was generated.
- the concentration of alanine was 4.5 mM, and the reaction yield was 1.8%.
- the concentrations of the respective substrates before entering the reactor were lactic acid: 0.155 M and aqueous ammonia: 0.715 M.
- the reaction time was 0.373 seconds, and the aqueous solution after the reaction was examined with a high performance liquid chromatography mass spectrometer. As a result, it was confirmed that amino groups were introduced into lactic acid and alanine was generated.
- the concentration of alanine was 5.5 mM, and the reaction yield was 3.6%.
- the concentrations of the respective substrates before entering the reactor were lactic acid: 0.325 M and aqueous ammonium acetate solution: 0.423 M.
- the reaction time was 0.293 seconds, and the aqueous solution after the reaction was examined with a high-performance liquid chromatography-mass spectrometer. As a result, it was confirmed that an amino group was introduced into lactic acid and alanine was generated.
- the concentration of alanine was 6. O mM, and the reaction yield was 1.8%.
- the concentrations of the respective substrates before entering the reactor were lactic acid: 0.3252 M and ammonium carbonate aqueous solution: 0.8071 M.
- the reaction time was 0.278 seconds.
- the concentration of alanine was 6.5 mM, and the reaction yield was 2.0%.
- the substrate concentrations before entering the reactor were tartaric acid: 0.3103 M and ammonia water: 1.4307 M.
- the reaction time was 0.22 seconds, and the aqueous solution after the reaction was examined with a high performance liquid chromatography mass spectrometer. It was confirmed that two amino groups were introduced into the lithic acid, and ⁇ , -diaminosuccinic acid was generated. The concentration of ⁇ , / 3-diaminosuccinic acid was 0.75 mM, and the reaction yield was 0.2%.
- reaction substrates Using lactic acid and aqueous ammonia as reaction substrates, we attempted to introduce amino groups into lactic acid under high-temperature, high-pressure water conditions.
- the reaction was performed in a batch reactor capable of shaking and stirring during the reaction shown in FIG.
- reaction tube having an inner volume of 1 0. 5 cm 3 as a reactor, the temperature 35 0, pressure 3 0 Set to be MP a, 6 0 seconds salt bath temperature of sodium nitrate Z potassium nitrate mixed salt
- the amino group was introduced to perform an amino group introduction reaction. It took 40 seconds to rise to the reaction temperature, and the reaction time was 40 seconds.
- the lactic acid concentration in the reaction solution before the reaction was 1.085 M and the aqueous ammonia concentration was 5.002 M: After the reaction, the obtained solution was examined with a high performance liquid chromatography mass spectrometer, and it was confirmed that 13.7 mM of alanine was produced. The reaction yield of alanine was 1.4%.
- Substrate solution (0.556 M lactic acid aqueous solution) Flow rate: 0.5 ml Zmin Substrate solution (liquefied ammonium) Flow rate: lml Zmin
- the concentration of each substrate in the reactor was 26.5 mM for lactic acid and 0.28 M for aqueous ammonia.
- the reaction time was 0.305 seconds, and the aqueous solution after the reaction was examined with a high-performance liquid chromatography-mass spectrometer. As a result, it was confirmed that an amino group was introduced into lactic acid and alanine was generated.
- the concentration of alanine was 5.4 mM, and the reaction yield was 20.4%.
- the present invention relates to a method for introducing an amino group, which comprises introducing an amino group into an organic acid by reacting the organic acid with ammonia or an ammonium salt compound under high temperature and high pressure water conditions.
- the present invention relates to a method for synthesizing an amino acid, which comprises reacting an organic acid with ammonia or an ammonium salt compound under high-pressure water conditions to synthesize an amino acid from the organic acid.
- An amino acid can be synthesized by reacting an organic acid and ammonia or an ammonium salt compound at a high temperature and a high pressure.3)
- the above-mentioned amino group introduction method can be applied to a flow system. 4)
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AU2002210968A AU2002210968A1 (en) | 2000-11-17 | 2001-10-30 | Method of introducing amino group and method of synthesizing amino acid |
EP01978942A EP1336603A4 (en) | 2000-11-17 | 2001-10-30 | METHOD OF INTRODUCING AMINO GROSSPS AND METHOD FOR SYNTHESIS OF AMINO ACIDS |
US10/416,494 US20040092725A1 (en) | 2000-11-17 | 2001-10-30 | Method of introducing amino group and method of synthesizing amino acid |
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JP2001309752A JP3762980B2 (ja) | 2000-11-17 | 2001-10-05 | アミノ基導入法及びアミノ酸の合成方法 |
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JP4798426B2 (ja) * | 2005-06-20 | 2011-10-19 | 独立行政法人産業技術総合研究所 | ヒドロキシカルボン酸の製造方法 |
JP2007320918A (ja) * | 2006-06-01 | 2007-12-13 | Mitsuyoshi Akatsuka | アミノ酸の製造方法 |
US9512061B2 (en) | 2011-12-19 | 2016-12-06 | Basf Se | Process for the preparation of racemic alpha-amino acids |
KR20140097586A (ko) * | 2011-12-19 | 2014-08-06 | 바스프 에스이 | 라세미 알파 아미노산의 제조 방법 |
CN105392773A (zh) | 2013-05-24 | 2016-03-09 | 巴斯夫欧洲公司 | 生产氨基酸的方法 |
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MX2020010831A (es) * | 2018-04-13 | 2020-10-28 | Archer Daniels Midland Co | Deshidratacion y aminacion de compuestos de alfa-, beta-dihidroxi carbonilo a alfa-aminoacidos. |
CN111018727A (zh) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | 甘氨酸的生产方法 |
CN109438283B (zh) * | 2018-12-25 | 2021-08-20 | 江苏兄弟维生素有限公司 | 一种β-氨基丙腈的合成方法及装置 |
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JPH05201940A (ja) * | 1991-11-25 | 1993-08-10 | Kao Corp | セリン又はその誘導体の製造方法 |
JPH06271518A (ja) * | 1993-03-19 | 1994-09-27 | Kao Corp | グリシンの製造方法 |
JPH06329605A (ja) * | 1993-05-25 | 1994-11-29 | Kao Corp | セリン又はその誘導体の製造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2734081A (en) * | 1956-02-07 | Preparation of | ||
US2956080A (en) * | 1953-06-01 | 1960-10-11 | Merck & Co Inc | Processes for preparing beta-alanine |
-
2001
- 2001-10-05 JP JP2001309752A patent/JP3762980B2/ja not_active Expired - Lifetime
- 2001-10-30 AU AU2002210968A patent/AU2002210968A1/en not_active Abandoned
- 2001-10-30 EP EP01978942A patent/EP1336603A4/en not_active Withdrawn
- 2001-10-30 WO PCT/JP2001/009499 patent/WO2002040442A1/ja not_active Application Discontinuation
- 2001-10-30 US US10/416,494 patent/US20040092725A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4350826A (en) * | 1977-05-26 | 1982-09-21 | Imperial Chemical Industries Limited | Process for preparing p-hydroxy phenylglycine |
JPH05201940A (ja) * | 1991-11-25 | 1993-08-10 | Kao Corp | セリン又はその誘導体の製造方法 |
JPH06271518A (ja) * | 1993-03-19 | 1994-09-27 | Kao Corp | グリシンの製造方法 |
JPH06329605A (ja) * | 1993-05-25 | 1994-11-29 | Kao Corp | セリン又はその誘導体の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113893570A (zh) * | 2021-06-11 | 2022-01-07 | 长春市吉达自动化系统有限公司 | 一种赖氨酸高效生产系统 |
CN113893570B (zh) * | 2021-06-11 | 2022-11-01 | 长春市吉达智慧工业科技有限公司 | 一种赖氨酸高效生产系统 |
Also Published As
Publication number | Publication date |
---|---|
JP3762980B2 (ja) | 2006-04-05 |
AU2002210968A1 (en) | 2002-05-27 |
JP2002212153A (ja) | 2002-07-31 |
US20040092725A1 (en) | 2004-05-13 |
EP1336603A1 (en) | 2003-08-20 |
EP1336603A4 (en) | 2005-11-16 |
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