CN111233704A - Method for preparing 6-aminocapronitrile product - Google Patents
Method for preparing 6-aminocapronitrile product Download PDFInfo
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- CN111233704A CN111233704A CN202010181800.3A CN202010181800A CN111233704A CN 111233704 A CN111233704 A CN 111233704A CN 202010181800 A CN202010181800 A CN 202010181800A CN 111233704 A CN111233704 A CN 111233704A
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- aminocapronitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
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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
- C07C227/22—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from lactams, cyclic ketones or cyclic oximes, e.g. by reactions involving Beckmann rearrangement
Abstract
The invention relates to a method for preparing a 6-aminocapronitrile product, which comprises the following steps: a: uniformly mixing caprolactam, an acid solution and the like according to a certain proportion, adding the mixture into a reaction kettle, heating and stirring the mixture for reaction; b: after the caprolactam in the step A is reacted, removing low-boiling-point substances under reduced pressure, and recrystallizing to obtain 6-aminocaproic acid salt; c: b, uniformly mixing the 6-aminocaproate, the alcohol, the ammoniating agent, the dehydrating agent and the like obtained in the step B according to a certain proportion, adding the mixture into a reaction kettle, heating and stirring the mixture for reaction; d: and D, rectifying the reaction liquid obtained in the step C, separating and purifying to obtain the 6-aminocapronitrile. The method for preparing the 6-aminocapronitrile product has the advantages of high reaction conversion rate, high purity of the 6-aminocapronitrile product up to more than 98%, mild reaction conditions and relatively simple preparation process.
Description
Technical Field
The invention relates to the technical field of preparation of aminonitrile, in particular to a method for preparing a 6-aminocapronitrile product.
Background
6-aminocapronitrile is an important chemical intermediate, the price is high, downstream products of 1, 6-hexamethylene diamine are obtained after hydrogenation, and the 1, 6-hexamethylene diamine is one of three nylon raw materials and can be used for producing nylon 66, nylon 610, hexamethylene diisocyanate and other large chemical products. The production of 6-aminocapronitrile is currently obtained mainly by partial hydrogenation of 1, 6-adiponitrile, as in patent CN1238334C, CN101309897B, or by hydrogenation of olefinic nitriles, as in patent NL 812780. The patent of preparing 6-aminocapronitrile by using caprolactam as a raw material is less, and the patent CN107602416A mentions a technology of preparing 6-aminocapronitrile by using a caprolactam gas phase method, but the technology requires that the reaction temperature is more than 300 ℃, and the pressure is applied, the reaction condition is harsh, and the technology is not suitable for large-scale industrialization; although patent CN107739318A mentions a caprolactam liquid-phase preparation process, the reaction conversion rate is low, and a large amount of nitrile solvent is used, which pollutes the environment.
Disclosure of Invention
The technical problem to be solved by the invention is a method for preparing a 6-aminocapronitrile product, which takes caprolactam as a raw material, and has the advantages of high reaction conversion rate, mild reaction conditions and relatively simple preparation process.
In order to solve the technical problems, the technical scheme adopted by the method for preparing the 6-aminocapronitrile product provided by the invention is as follows:
a process for preparing a 6-aminocapronitrile product comprising the steps of:
a: uniformly mixing caprolactam and an acidic solution, adding the mixture into a reaction kettle, heating and stirring the mixture to react;
b: after the caprolactam in the step A is reacted, distilling to remove low-boiling-point substances, and recrystallizing to obtain 6-aminocaproic acid salt;
c: b, uniformly mixing the 6-aminocaproate obtained in the step B with alcohol, an ammoniating agent and a dehydrating agent, and adding the mixture into a reaction kettle to be heated and stirred for reaction;
d: and D, rectifying the reaction liquid obtained in the step C under reduced pressure, separating and purifying to obtain the 6-aminocapronitrile.
Preferably, the acidic solution of step a is an aqueous solution of an organic acid, which is formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or a combination thereof.
Preferably, in the step A, the mass ratio of the caprolactam to the acidic solution is 1 (1-100). Preferably, in the step A, the mass ratio of the caprolactam to the acidic solution is 1 (1-20).
Preferably, in step B, the solvent for recrystallization comprises a good solvent and a poor solvent, the volume ratio of the good solvent to the poor solvent is 1 (0.1-1), the good solvent is water, methanol, ethylene glycol or dimethylformamide or a combination thereof, and the poor solvent is petroleum ether, cyclohexane, toluene, p-xylene or butyl acetate or a combination thereof.
Further preferably, in step B, in the recrystallization process: the stirring speed is 150-200 r/min, and the cooling speed is 1-5 ℃/min.
Preferably, in step C, the alcohol is a diol, and the diol is ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 4-pentanediol, 1, 5-pentanediol or a combination thereof.
Preferably, in step C, the ammoniating agent is ammonium oxalate, formamide, ammonium carbamate, or a combination thereof.
Preferably, in step C, the dehydrating agent is phosphorus oxychloride, phosphorus pentachloride, ethyl phosphate, trifluoroacetic anhydride, N-methyl-N-trimethylsilyl trifluoroacetamide, or a combination thereof.
Preferably, in the step C, the mass ratio of the 6-aminocaproate to the alcohol to the ammoniating agent to the dehydrating agent is 1 (1-10) to 1-8 to 0.01-0.1.
Preferably, in step D, the vacuum rectification conditions of the reaction solution are as follows: the temperature of the bottom of the vacuum distillation tower is 180-plus-190 ℃, the vacuum degree is more than-0.095 MPa, when the temperature of the top of the distillation tower is 40-60 ℃, the low-boiling-point substances begin to be discharged, and when the temperature of the top of the distillation tower is 160-plus-170 ℃, the 6-aminocapronitrile begins to be discharged.
The invention relates to a method for preparing 6-aminocapronitrile product by reacting caprolactam in liquid phase, which comprises the following steps:
wherein HX is aqueous solution of organic acid, and the aqueous solution of organic acid can be aqueous solution of one or more mixed acids of formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
Wherein R is1Is an alkyl chain of 2 to 5 carbon atoms; NH (NH)3R2The ammonia source can be one or a combination of more than two of ammonium oxalate, formamide and ammonium carbamate. Independently, R2Represents a non-amino group of the ammonia source material.
Compared with the prior art, the method for preparing the 6-aminocapronitrile product has the following advantages:
1. the method for preparing the 6-aminocapronitrile product takes caprolactam as a starting raw material, and 6-aminocapronitrile is prepared by reaction in a liquid phase in the absence of a catalyst.
2. Caprolactam is hydrolyzed in an acid solution to open a ring to form 6-aminocaproic acid salt, if the caprolactam is directly hydrolyzed without adding acid, the obtained 6-aminocaproic acid is unstable and easy to cyclize, the subsequent process is difficult to carry out, and the used acid is dissolved in water to enable the reaction to be in a homogeneous reaction, so that the salt forming reaction effect is better. The acidic aqueous solution needs to be excessive so as to ensure that the caprolactam is completely hydrolyzed, ring-opened and salified.
3. In the step B, the recrystallization has the advantages that the purity of the 6-aminocaproate can be greatly improved, a high-purity main raw material is provided for the reaction in the subsequent step C, and unnecessary side reactions are reduced.
4. In the step C, 6-aminocaproate and dihydric alcohol are subjected to esterification reaction, and hydroxyl-terminated dihydric alcohol is adopted, so that the reactivity of the alcohol is improved, the feeding amount of the alcohol is reduced, and the purification unit consumption is saved. The ammoniating agent is ammonium oxalate, formamide, ammonium carbamate or a combination thereof, can release ammonia to participate in ammoniation reaction after being heated and decomposed, and terminal amino groups in a molecular structure of the ammoniating agent can also participate in ammoniation reaction. The dehydrating agent is phosphorus oxychloride, phosphorus pentachloride, ethyl phosphate, trifluoroacetic anhydride, N-methyl-N-trimethylsilyl trifluoroacetamide or a combination thereof, and is used as the dehydrating agent for the ammoniated reaction product, so that the ammoniated product is subjected to dehydration reaction to generate 6-aminocapronitrile, and the ammoniated product is difficult to undergo dehydration reaction without adding the substances. The alcohol excess ensures that the 6-aminocaproate is completely esterified; the excess amination agent ensures complete amination of the esterification product.
Drawings
FIG. 1 is a nuclear magnetic detection diagram (hydrogen spectrum) of a 6-aminocapronitrile product produced in the method for producing 6-aminocapronitrile according to example 1 of the present invention;
FIG. 2 is a nuclear magnetic detection diagram (carbon spectrum) of a 6-aminocapronitrile product produced in the method for producing 6-aminocapronitrile according to example 1 of the present invention;
FIG. 3 is a gas chromatographic examination of the 6-aminocapronitrile product produced in the process for producing 6-aminocapronitrile according to example 1 of the invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The experimental reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are conventional methods unless otherwise specified.
Examples 1 to 5 below are examples of the preparation of 6-aminocapronitrile from caprolactam under laboratory conditions, the vacuum distillation conditions being typical distillation conditions in the laboratory, the column of a glass distillation column used in the laboratory having a height of 1.2m and an internal diameter of 24mm, and the packing being a 3mm diameter Φ ring. The temperature of the bottom of the vacuum distillation tower is 180 ℃ plus 190 ℃, the vacuum degree is more than-0.095 MPa, and when the temperature of the top of the distillation tower is 160 ℃ plus 170 ℃, the 6-aminocapronitrile begins to be discharged.
Example 1
Uniformly mixing 10g of caprolactam and 100g of formic acid aqueous solution, adding the mixture into a reaction kettle A, stirring and heating at a stirring speed of 1000RPM, starting reflux reaction when the temperature rises to 110 ℃, discharging the reaction solution to a rectifying kettle C after refluxing for 2h, distilling to remove low-boiling-point substances, transferring the rectifying kettle solution to a reaction kettle B, recrystallizing by using methanol-toluene (the volume ratio of the methanol to the toluene is 1: 0.8) (the stirring speed is 180 r/min, the cooling speed is 2.5 ℃/min) to obtain 6-aminocaproate solid, discharging the liquid in the kettle, adding 30g of ethylene glycol, 25g of ammonium oxalate and 1g of phosphorus oxychloride into the kettle, uniformly mixing, stirring and heating at a stirring speed of 1000RPM, and carrying out reflux reaction at 105 ℃ for 3h, and then discharging. After the reaction is finished, the reaction liquid is rectified under reduced pressure, separated and purified to obtain the 6-aminocapronitrile with the purity of 98.3 percent and the product yield of 68.9 percent.
The vacuum rectification conditions of the 6-aminocapronitrile product in the example are as follows: the temperature of the rectifying still is 183 ℃, the top temperature is 161 ℃, the vacuum degree is-0.096 MPa, and the 6-aminocapronitrile is distilled from the top of the rectifying still.
Example 2
Uniformly mixing 10g of caprolactam and 150g of formic acid aqueous solution, adding the mixture into a reaction kettle A, stirring and heating at a stirring speed of 1100RPM, starting reflux reaction when the temperature is raised to 112 ℃, refluxing for 1.5h, discharging the reaction solution to a rectifying kettle C, distilling to remove low-boiling-point substances, transferring the rectifying kettle solution to a reaction kettle B, recrystallizing ethylene glycol-toluene (the volume ratio of the ethylene glycol to the toluene is 1: 0.5) at a stirring speed of 150 r/min and a cooling speed of 2 ℃/min to obtain 6-aminocaproate solid, discharging the liquid in the kettle, adding 40g of ethylene glycol, 35g of ammonium oxalate and 0.5g of ethyl phosphate into the kettle, uniformly mixing, stirring and heating at a stirring speed of 1100RPM, refluxing at 150 ℃ for 5h, and discharging. After the reaction is finished, the reaction liquid is rectified under reduced pressure, separated and purified to obtain the 6-aminocapronitrile with the purity of 98.8 percent and the product yield of 70.5 percent.
The vacuum rectification conditions of the 6-aminocapronitrile product in the example are as follows: the temperature of the rectifying still is 189 ℃, the top temperature is 160 ℃, the vacuum degree is-0.095 MPa, and the 6-aminocapronitrile is distilled from the top of the rectifying still.
Example 3
Uniformly mixing 11g of caprolactam and 155g of acetic acid aqueous solution, adding the mixture into a reaction kettle A, stirring and heating at a stirring speed of 1200RPM, starting reflux reaction when the temperature is raised to 110 ℃, discharging the reaction solution to a rectifying kettle C after refluxing for 3 hours, distilling to remove low-boiling-point substances, transferring the rectifying kettle solution to a reaction kettle B, recrystallizing by using methanol-p-xylene (the volume ratio of the methanol to the p-xylene is 1: 0.8) (the stirring speed is 190 r/min, and the cooling speed is 3.5 ℃/min) to obtain 6-aminocaproate solid, discharging the liquid in the kettle, adding 40g of ethylene glycol, 35g of formamide and 0.6g of ethyl phosphate into the kettle, uniformly mixing, stirring and heating at a stirring speed of 1200RPM, and carrying out reflux reaction at 130 ℃ for 2 hours, and then discharging. After the reaction is finished, the reaction liquid is rectified under reduced pressure, separated and purified to obtain the 6-aminocapronitrile with the purity of 99.1 percent and the product yield of 73 percent.
The vacuum rectification conditions of the 6-aminocapronitrile product in the example are as follows: the temperature of the rectifying still is 185 ℃, the top temperature is 162 ℃, the vacuum degree is-0.095 MPa, and the 6-aminocapronitrile is distilled from the top of the tower.
Example 4
Uniformly mixing 11g of caprolactam and 120g of methanesulfonic acid aqueous solution, adding the mixture into a reaction kettle A, stirring and heating at a stirring speed of 1100RPM, starting reflux reaction when the temperature is raised to 110 ℃, discharging the reaction solution to a rectifying kettle C after refluxing for 2 hours, distilling to remove low-boiling-point substances, transferring the rectifying kettle solution to a reaction kettle B, recrystallizing by using methanol-cyclohexane (the volume ratio of the methanol to the cyclohexane is 1: 0.4) (the stirring speed is 190 r/min, the cooling speed is 4 ℃/min) to obtain 6-aminocaproate solid, discharging the liquid in the kettle, adding 40g of 1, 3-propylene glycol, 35g of formamide and 0.5g of trifluoroacetic anhydride into the kettle, uniformly mixing, stirring and heating at a stirring speed of 1200RPM, and carrying out reflux reaction at 130 ℃ for 2.5 hours, and discharging. After the reaction is finished, the reaction liquid is rectified under reduced pressure, separated and purified to obtain the 6-aminocapronitrile with the purity of 98.1 percent and the product yield of 68.9 percent.
The vacuum rectification conditions of the 6-aminocapronitrile product in the example are as follows: the temperature of the rectifying still is 183 ℃, the top temperature is 162 ℃, the vacuum degree is-0.098 MPa, and the 6-aminocapronitrile is distilled from the top of the rectifying still.
Example 5
Uniformly mixing 10g of caprolactam and 145g of benzenesulfonic acid aqueous solution, adding the mixture into a reaction kettle A, stirring and heating at the stirring speed of 1100RPM, starting reflux reaction when the temperature is raised to 115 ℃, discharging the reaction solution to a rectifying kettle C after refluxing for 3 hours, distilling to remove low-boiling-point substances, transferring the rectifying kettle solution to a reaction kettle B, recrystallizing by using dimethylformamide-petroleum ether (the volume ratio of dimethylformamide to petroleum ether is 1: 0.8) (the stirring speed is 200 r/min, and the cooling speed is 3 ℃/min) to obtain 6-aminocaproate solid, discharging the liquid in the kettle, adding 60g of 1, 4-butanediol, 50g of ammonium carbamate and 0.8g of phosphorus oxychloride into the kettle, uniformly mixing, stirring and heating, stirring at the stirring speed of 1100RPM, carrying out reflux reaction at 120 ℃ for 2 hours, and discharging. After the reaction is finished, the reaction liquid is rectified under reduced pressure, separated and purified to obtain the 6-aminocapronitrile with the purity of 99.2 percent and the product yield of 66.8 percent.
The vacuum rectification conditions of the 6-aminocapronitrile product in the example are as follows: the temperature of the rectifying still is 186 ℃, the top temperature is 160 ℃, the vacuum degree is-0.098 MPa, and the 6-aminocapronitrile is distilled from the top of the rectifying still.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A process for preparing a 6-aminocapronitrile product, comprising the steps of:
a: uniformly mixing caprolactam and an acidic solution, adding the mixture into a reaction kettle, heating and stirring the mixture to react;
b: after the caprolactam in the step A is reacted, distilling to remove low-boiling-point substances, and recrystallizing to obtain 6-aminocaproic acid salt;
c: b, uniformly mixing the 6-aminocaproate obtained in the step B with alcohol, an ammoniating agent and a dehydrating agent, and adding the mixture into a reaction kettle to be heated and stirred for reaction;
d: and D, rectifying the reaction liquid obtained in the step C under reduced pressure, separating and purifying to obtain the 6-aminocapronitrile.
2. The method of claim 1, wherein: the acidic solution in step A is an aqueous solution of an organic acid, and the aqueous solution of the organic acid is formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or a combination thereof.
3. The method of claim 1, wherein: in the step A, the mass ratio of caprolactam to the acid solution is 1 (1-100).
4. The method of claim 1, wherein: in the step A, the mass ratio of caprolactam to the acid solution is 1 (1-20).
5. The method of claim 1, wherein: in the step B, the solvent for recrystallization comprises a good solvent and a poor solvent, the volume ratio of the good solvent to the poor solvent is 1 (0.1-1), the good solvent is water, methanol, ethylene glycol or dimethylformamide or a combination thereof, and the poor solvent is petroleum ether, cyclohexane, toluene, p-xylene or butyl acetate or a combination thereof.
6. The method of claim 1, wherein: in the step C, the alcohol is dihydric alcohol, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 4-pentanediol, 1, 5-pentanediol or a combination thereof.
7. The method of claim 1, wherein: in step C, the ammoniating agent is ammonium oxalate, formamide, ammonium carbamate, or a combination thereof.
8. The method of claim 1, wherein: in the step C, the dehydrating agent is phosphorus oxychloride, phosphorus pentachloride, ethyl phosphate, trifluoroacetic anhydride, N-methyl-N-trimethylsilyl trifluoroacetamide or a combination thereof.
9. The method of claim 1, wherein: in the step C, the mass ratio of the 6-aminocaproate to the alcohol to the ammoniating agent to the dehydrating agent is 1 (1-10) to 1-8 to 0.01-0.1.
10. The method of claim 1, wherein: in the step D, the vacuum rectification conditions of the reaction liquid are as follows: the temperature of the bottom of the vacuum distillation tower is 180-plus-190 ℃, the vacuum degree is more than-0.095 MPa, when the temperature of the top of the distillation tower is 40-60 ℃, the low-boiling-point substances begin to be discharged, and when the temperature of the top of the distillation tower is 160-plus-170 ℃, the 6-aminocapronitrile begins to be discharged.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111574400A (en) * | 2020-06-10 | 2020-08-25 | 江苏扬农化工集团有限公司 | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine |
CN114149331A (en) * | 2021-12-20 | 2022-03-08 | 昌德新材科技股份有限公司 | Method for preparing hexamethylene diamine |
CN114195663A (en) * | 2021-12-20 | 2022-03-18 | 昌德新材科技股份有限公司 | Preparation method of 6-aminocaproic acid |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5839653A (en) * | 1981-08-13 | 1983-03-08 | ヘミツシエ・ウエルケ・ヒユ−ルス・アクチエン・ゲゼルシヤフト | Manufacture of fatty nitrile |
JP2000007637A (en) * | 1998-06-25 | 2000-01-11 | Kao Corp | Production of aliphatic nitrile |
JP2002284753A (en) * | 2001-03-23 | 2002-10-03 | Koei Chem Co Ltd | Method for manufacturing nitrile |
US20030158256A1 (en) * | 2000-05-15 | 2003-08-21 | Cowen Scott Douglas | N-substituted peptidyl nitriles as cysteine cathepsin inhibitors |
JP2006182708A (en) * | 2004-12-28 | 2006-07-13 | Kao Corp | Manufacturing method of aliphatic nitrile |
WO2012119941A1 (en) * | 2011-03-04 | 2012-09-13 | Prozymex A/S | Peptidyl nitrilcompounds as peptidase inhibitors |
US20140039219A1 (en) * | 2012-08-03 | 2014-02-06 | Sunny Pharmtech Inc. | Method of Making 6-Aminocaproic Acid As Active Pharmaceutical Ingredient |
CN104684901A (en) * | 2012-07-25 | 2015-06-03 | 索瓦制药公司 | Cystathionine-y-gamma-lyase (cse) inhibitors |
CN104945278A (en) * | 2015-06-04 | 2015-09-30 | 荆州和乐实业科技有限公司 | Malononitrile synthesis method |
CN109369430A (en) * | 2018-11-22 | 2019-02-22 | 沧州旭阳化工有限公司 | A method of preparing 6-aminocaprolc acid |
CN110423201A (en) * | 2019-04-30 | 2019-11-08 | 郑州大学 | A method of using caprolactam as Material synthesis hexamethylene diamine |
WO2020031201A1 (en) * | 2018-08-04 | 2020-02-13 | Msn Laboratories Private Limited, R&D Center | Improved process for the preparation of 6-aminohexanoic acid |
-
2020
- 2020-03-16 CN CN202010181800.3A patent/CN111233704B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5839653A (en) * | 1981-08-13 | 1983-03-08 | ヘミツシエ・ウエルケ・ヒユ−ルス・アクチエン・ゲゼルシヤフト | Manufacture of fatty nitrile |
JP2000007637A (en) * | 1998-06-25 | 2000-01-11 | Kao Corp | Production of aliphatic nitrile |
US20030158256A1 (en) * | 2000-05-15 | 2003-08-21 | Cowen Scott Douglas | N-substituted peptidyl nitriles as cysteine cathepsin inhibitors |
JP2002284753A (en) * | 2001-03-23 | 2002-10-03 | Koei Chem Co Ltd | Method for manufacturing nitrile |
JP2006182708A (en) * | 2004-12-28 | 2006-07-13 | Kao Corp | Manufacturing method of aliphatic nitrile |
WO2012119941A1 (en) * | 2011-03-04 | 2012-09-13 | Prozymex A/S | Peptidyl nitrilcompounds as peptidase inhibitors |
CN104684901A (en) * | 2012-07-25 | 2015-06-03 | 索瓦制药公司 | Cystathionine-y-gamma-lyase (cse) inhibitors |
US20140039219A1 (en) * | 2012-08-03 | 2014-02-06 | Sunny Pharmtech Inc. | Method of Making 6-Aminocaproic Acid As Active Pharmaceutical Ingredient |
CN104945278A (en) * | 2015-06-04 | 2015-09-30 | 荆州和乐实业科技有限公司 | Malononitrile synthesis method |
WO2020031201A1 (en) * | 2018-08-04 | 2020-02-13 | Msn Laboratories Private Limited, R&D Center | Improved process for the preparation of 6-aminohexanoic acid |
CN109369430A (en) * | 2018-11-22 | 2019-02-22 | 沧州旭阳化工有限公司 | A method of preparing 6-aminocaprolc acid |
CN110423201A (en) * | 2019-04-30 | 2019-11-08 | 郑州大学 | A method of using caprolactam as Material synthesis hexamethylene diamine |
Non-Patent Citations (2)
Title |
---|
王金英 等: "《有机化学实验教程》", 31 July 2019, 中国医药科技出版社 * |
韩广甸: "《有机制备化学手册 中,》", 31 May 1980, 石油化学工业出版社 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111574400A (en) * | 2020-06-10 | 2020-08-25 | 江苏扬农化工集团有限公司 | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine |
CN111574400B (en) * | 2020-06-10 | 2022-11-25 | 江苏扬农化工集团有限公司 | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine |
CN114149331A (en) * | 2021-12-20 | 2022-03-08 | 昌德新材科技股份有限公司 | Method for preparing hexamethylene diamine |
CN114195663A (en) * | 2021-12-20 | 2022-03-18 | 昌德新材科技股份有限公司 | Preparation method of 6-aminocaproic acid |
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