CN109593045B - Preparation method of 11-aminoundecanoic acid - Google Patents
Preparation method of 11-aminoundecanoic acid Download PDFInfo
- Publication number
- CN109593045B CN109593045B CN201710924314.4A CN201710924314A CN109593045B CN 109593045 B CN109593045 B CN 109593045B CN 201710924314 A CN201710924314 A CN 201710924314A CN 109593045 B CN109593045 B CN 109593045B
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- reaction
- oxo
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of 11-aminoundecanoic acid, which comprises the following steps: 1) dissolving 9-hydroxynonanoic acid or 9-hydroxynonanoate in a solvent, and carrying out selective oxidation in the presence of an oxidant to prepare 9-oxononanoic acid or 9-oxononanoate; 2) dissolving the 9-oxo-nonanoic acid or 9-oxo-nonanoate and cyanoacetate in a solvent, and carrying out knoevenagel condensation reaction to obtain a compound shown in a formula III; 3) continuing to perform hydrolysis reaction on the product obtained in the step 2), and acidifying to obtain 2-cyano-undec-2-enedioic acid; 4) carrying out selective decarboxylation reaction on the product obtained in the step 3) to obtain a compound 10-cyano-10-alkene decanoic acid shown in the formula V; 5) adding a catalyst into the 10-cyano-10-alkene decanoic acid obtained in the step 4), replacing the mixture by nitrogen and hydrogen in sequence, carrying out hydrogenation reduction reaction, and refining a crude product to obtain the 11-aminoundecanoic acid.
Description
Technical Field
The invention relates to the field of nylon materials, in particular to a preparation method of a nylon 11 material monomer 11-aminoundecanoic acid.
Background
The 11-aminoundecanoic acid is a multipurpose organic intermediate and a monomer of nylon-11, the nylon-11 has the characteristics of high strength, temperature resistance, wear resistance, good chemical stability, excellent electrical insulation performance and the like, and particularly has high impact resistance strength, light specific gravity, low water absorption, easy processing and forming and no toxicity to human bodies at low temperature; the method is widely applied to the fields of automobile industry, ordnance industry, cable industry, city gas engineering, electrical appliance industry, powder coating, modified composite materials and the like. The technical key of nylon 11 lies in the preparation of monomer 11-aminoundecanoic acid, and the quality of the monomer directly affects the quality of the polymer and the yield of the product, so that the development of a reasonable 11-aminoundecanoic acid preparation process is of great importance.
Some studies on 11-aminoundecanoic acid have been made in the prior art, for example, chinese patent application publications CN101289409A and CN102702525A disclose a preparation method of 11-aminoundecanoic acid, in which castor oil reacts with methanol to produce castor oil methyl ester, which is then cracked and fractionated under reduced pressure to obtain undecylenic acid and heptaldehyde, undecylenic acid is added with hydrobromic acid in the presence of hydrogen peroxide to produce mahalanobis addition reaction to produce 11-bromoundecanoic acid, which is then nucleophilic-substituted with ammonia water to obtain the product 11-aminoundecanoic acid.
Chinese patent application publications CN104499081A, CN104499082A and CN104562340A disclose a method for preparing aminoundecanoic acid, bromoundecanoic acid and 15 wt% ammonia water are added into a reactor, stirred and reacted at room temperature, then the reaction product is heated and distilled, cold water is used for absorbing ammonia gas, the heating and distillation temperature is 60 ℃, the distillation is stopped until no bubble is generated, then cooling and suction filtration are carried out, a filter cake is washed by deionized water until no bromide ion is generated, a silver nitrate solution is adopted for detection, and the product is dried in vacuum to obtain the product 11-aminoundecanoic acid.
The existing production method of 11-amino undecanoic acid has a plurality of defects, wherein the cracking belongs to a high energy consumption process, high temperature condition is needed, the cracking is not thorough, side reactions are more, coking is easy to occur, the product yield is low, the separation is difficult due to the easy occurrence of ectopic double bond of the intermediate 10-undecylenic acid, hydrobromic acid used in the bromination process is easy to pollute the environment, the reaction time of 11-bromoundecanoic acid and ammonia water is long, and in order to improve the quality and the yield of the product 11-amino undecanoic acid, the ammonia water is usually needed to be greatly excessive, so a large amount of ammonia water needs to be recovered in the post-treatment, and the production cost is increased. In general, the process has long reaction time, complicated engineering devices, high production cost and more three wastes, so that a new process for developing the 11-aminoundecanoic acid is urgently needed.
U.S. patent application publication No. 2016/0002147 reports the use of an olefin metathesis reaction with an unsaturated fatty acid and an acrylonitrile feedstock, the resulting intermediate being reduced by hydrogenation to produce 11-aminoundecanoic acid.
Patent application publication WO2012/095575a1 of arkema, france reports a process for the preparation of 11-aminoundecanoic acid by oxidation of an unsaturated fatty acid to form a nitrile compound, which is then reduced by hydrogenation to give the product 11-aminoundecanoic acid.
The methods reported in the two patents have high requirements on catalysts, and the reaction conditions are very harsh, so that the method is not suitable for industrial production.
Disclosure of Invention
Technical problem
The invention aims to provide a preparation method of 11-aminoundecanoic acid, which overcomes the defects of long reaction time, harsh conditions, more byproducts and difficult separation of products in the traditional process.
Technical scheme
The invention provides a preparation method of 11-aminoundecanoic acid, which comprises the following steps:
1) dissolving the compound 9-hydroxy nonanoic acid or 9-hydroxy nonanoate in a solvent, and selectively oxidizing under the action of an oxidant to prepare the compound 9-oxo nonanoic acid or 9-oxo nonanoate in the formula II;
2) dissolving the 9-oxo-nonanoic acid or 9-oxo-nonanoate and cyanoacetate in a solvent, and carrying out knoevenagel condensation reaction under the action of a catalyst to obtain a compound shown in a formula III;
3) carrying out hydrolysis reaction on the compound of the formula III obtained in the step 2) under the action of a basic catalyst, and adding acid for acidification after the hydrolysis reaction is finished to obtain a compound of a formula IV, namely 2-cyanoundecane-2-enedioic acid;
4) carrying out selective decarboxylation reaction on the 2-cyano-undec-2-enedioic acid obtained in the step 3) to obtain a compound 10-cyano-10-ene decanoic acid shown in the formula V;
5) adding a catalyst into the 10-cyano-10-alkene decanoic acid obtained in the step 4), replacing the mixture by nitrogen and hydrogen in sequence, carrying out hydrogenation reduction reaction to obtain 11-aminoundecanoic acid,
wherein R is1Is H, or straight or branched C1-C10An alkyl group; preferably H, or C which is linear or branched1-C6Alkyl, more preferably H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or pentyl; and R2Is straight-chain or branched C1-C10Alkyl, preferably straight or branched C1-C6More preferably, the alkyl group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group or a pentyl group.
Wherein, in step 1):
the oxidant is manganese dioxide, copper oxide or zinc oxide, and the molar ratio of the oxidant to 9-hydroxynonanoic acid or 9-hydroxynonanoate is 1.0-2.0, preferably 1.0-1.2;
the solvent may be one capable of dissolving 9-hydroxynonanoic acid or 9-hydroxynonanoate, without particular limitation, and examples thereof include, but are not limited to, ethyl acetate, tetrahydrofuran, N-dimethylformamide, or dioxane;
the reaction temperature is 20-80 ℃, preferably 25-50 ℃; the reaction time is 5-12 h, preferably 8-10 h;
the 9-hydroxynonanoate is methyl 9-hydroxynonanoate, ethyl 9-hydroxynonanoate, propyl 9-hydroxynonanoate, isopropyl 9-hydroxynonanoate or butyl 9-hydroxynonanoate;
in step 2):
the catalyst of the knoevenagel condensation reaction is a base, examples of which include, but are not limited to, triethylamine, N-diisopropylethylamine, N-methylmorpholine, tetramethylethylenediamine, potassium hydroxide, sodium hydroxide or piperidine, and the molar ratio of the catalyst of the knoevenagel condensation reaction to 9-oxononanoic acid or 9-oxononanoate is 0.1 to 3.0, preferably 0.1 to 2.0, particularly preferably 0.1 to 0.5 when the base is an organic base;
the cyanoacetate is added in an amount such that the molar ratio of 9-oxononanoic acid or 9-oxononanoate to cyanoacetate is 0.8-1.5: 1.0;
the solvent is not particularly limited as long as it can dissolve the cyanoenoic acid, and examples thereof include, but are not limited to, dioxane, ethyl acetate, tetrahydrofuran;
the knoevenagel condensation reaction temperature is 25-50 ℃, and the reaction lasts 10-12 h;
the cyanoacetate is methyl cyanoacetate, ethyl cyanoacetate, propyl cyanoacetate or isopropyl cyanoacetate;
in step 3):
the alkaline catalyst for the hydrolysis reaction is an aqueous solution of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the dosage of the catalyst is that the molar ratio of the catalyst to 9-oxo-nonanoic acid or 9-oxo-nonanoate is 1.0-2.5: 1.0; the acids used for acidification are those commonly used in the art and include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid;
in step 4):
the selective decarboxylation of the 2-cyanoundec-2-enedioic acid may be carried out with or without a catalyst, which may be concentrated sulfuric acid or a base (e.g., sodium hydroxide, lithium hydroxide, or potassium hydroxide); when the catalyst is concentrated sulfuric acid, the catalyst is used in a catalytic amount, such as 1 weight per thousand-1 percent of the amount of the 2-cyanoundec-2-enedioic acid; when the catalyst is alkali, the molar ratio of the catalyst to the 2-cyano-undec-2-enedioic acid is 1.0-2.5: 1.0, the reaction temperature is 100-120 ℃, and the reaction time is 3-5 h; the solvent used in step 4) may be dioxane, N-dimethylformamide and dimethylsulfoxide.
In step 5):
the catalyst for the hydrogenation reduction reaction can be Raney nickel, platinum carbon or palladium carbon, and the mass ratio of the dosage of the catalyst for the hydrogenation reduction reaction to the 2-cyanoundec-2-enedioic acid is 0.001-0.1, preferably 0.001-0.05; the system of the hydrogenation reduction reaction keeps the hydrogen partial pressure of 1.0-6.0 Mpa, and the reaction lasts for 1-5 h at the temperature of 100-120 ℃.
Advantageous effects
The preparation method of the 11-aminoundecanoic acid provided by the invention has the characteristics of short process route, simplicity, easy operation and the like, avoids high-energy-consumption pyrolysis, severe-pollution bromination, ammoniation and other operation units, belongs to a green and environment-friendly process, has less consumption of condensation reaction catalysts, reduces the production cost, has simple post-treatment and easy operation, and is suitable for industrial production.
Detailed Description
The present invention will be further illustrated by the following examples, which are included to assist in understanding the present invention, and are not intended to limit the true scope of the invention in any way, including but not limited to the following:
example 1
Preparation of methyl 9-oxononanoate
Mixing methyl 9-hydroxynonanoate (37.6g, 0.2mol) with MnO2(17.4g, 0.2mol) is put into a reaction kettle, 200ml ethyl acetate is added, stirring is started, 180 r/min is carried out, the temperature is 50 ℃, the reaction progress is monitored in real time, the temperature is reduced to room temperature after 8h, filtration is carried out, the solvent is distilled out under reduced pressure, and 35.3g of off-white solid product (m/z: 186) is obtained after refining treatment.
Preparation of cyanoolefine acid
Putting methyl 9-oxo-nonanoate (18.6g, 0.1mol), methyl cyanoacetate (9.9g, 0.1mol) and triethylamine (3.5g, 35.0mmol) into a reaction kettle, adding 100ml dioxane (1,4-dioxane), starting stirring, rotating at 180 rpm, monitoring the reaction process in real time at 50 ℃, cooling to room temperature after 12h, adding 80ml 10 wt% sodium hydroxide aqueous solution for hydrolysis, acidifying with 1N hydrochloric acid, and refining to obtain 21.2g pale yellow cyanoolefine acid product.
Preparation of decarboxylated intermediates
Placing 10g of cyanoolefine acid into a high-pressure kettle, adding 50ml of dioxane and a catalytic amount of concentrated sulfuric acid, starting stirring, rotating at 180 r/min, carrying out decarboxylation reaction at 100 ℃, monitoring the reaction process by TLC, cooling to room temperature after 3h, separating the catalyst, and directly using the crude product in the next step.
Preparation of 11-aminoundecanoic acid
Adding 5 wt% Raney Ni catalyst (RTH-3110 type, large communication chemical company, Ltd.) into the decarboxylated reaction system, closing the reaction kettle, replacing with nitrogen and hydrogen in sequence, keeping the hydrogen partial pressure at 3Mpa, starting stirring, 180 r/m, raising the temperature to 100 ℃ by program, reacting for 5h, then cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling under reduced pressure to obtain dioxane, washing and refining the crude product with water to obtain 6.3g of 11-aminoundecanoic acid, which is white powder in appearance and has the purity of 98.0% and the melting point of 189 ℃ (lit.), (m/z: 201).
Example 2
Preparation of methyl 9-oxononanoate
Mixing methyl 9-hydroxynonanoate (37.6g, 0.2mol) with MnO2(17.4g, 0.2mol) was placed in a reaction vessel, 200ml of ethyl acetate was added, stirring was turned onStirring at 180 rpm, monitoring the reaction progress in real time at 25 deg.C, cooling to room temperature after 10 hr, filtering, distilling off solvent under reduced pressure, and refining to obtain 33.1g of white-like solid product (m/z: 186).
Preparation of cyanoolefine acid
Putting methyl 9-oxo-nonanoate (18.6g, 0.1mol) and methyl cyanoacetate (9.9g, 0.1mol) into a reaction kettle, adding 100ml of dioxane and 115ml of 10 wt% potassium hydroxide aqueous solution, starting stirring, rotating at 180 rpm at 25 ℃, monitoring the reaction progress in real time, cooling to room temperature after 10h, distilling the dioxane under reduced pressure, acidifying with 1N hydrochloric acid, extracting with ethyl acetate, desolventizing, and refining to obtain 20.5g of yellow cyanoolefine acid product.
Preparation of decarboxylated intermediates
Placing 10g of cyanoolefine acid into an autoclave, adding 50ml of dioxane, starting stirring, rotating at 180 rpm, carrying out decarboxylation reaction at 100 ℃, monitoring the reaction process by TLC, cooling to room temperature after 5h, and directly using the crude product in the next step.
Preparation of 11-aminoundecanoic acid
Adding 5 wt% of Raney nickel catalyst (ZL-N311 type, Zhongshan city catalyst factory) into the decarboxylated reaction system, closing the reaction kettle, sequentially replacing with nitrogen and hydrogen, keeping the hydrogen partial pressure at 3Mpa, starting stirring, rotating at 180 rpm, raising the temperature to 100 ℃ by program, reacting for 5 hours, then cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling under reduced pressure to obtain dioxane, washing and refining the crude product with water to obtain 5.7g of 11-aminoundecanoic acid, wherein the appearance is white powder, the purity is 99.2%, and the melting point is 190 ℃ (lit.), (m/z: 201).
Example 3
Preparation of methyl 9-oxononanoate
Putting 9-hydroxy nonanoic acid methyl ester (37.6g, 0.2mol) and CuO (15.9g, 0.2mol) into a reaction kettle, adding 200ml of tetrahydrofuran, starting stirring, rotating at 180 r/min, monitoring the reaction progress in real time, cooling to room temperature after 10h, filtering, distilling off the solvent under reduced pressure, and refining to obtain 30.1g of an off-white solid product (m/z: 186).
Preparation of cyanoolefine acid
Putting methyl 9-oxo-nonanoate (18.6g, 0.1mol) and methyl cyanoacetate (9.9g, 0.1mol) into a reaction kettle, adding 100ml of dioxane and 80ml of 10 wt% sodium hydroxide aqueous solution, starting stirring, rotating at 180 rpm, monitoring the reaction process in real time at 25 ℃, cooling to room temperature after 10h, distilling the dioxane under reduced pressure, acidifying with 1N hydrochloric acid, extracting with ethyl acetate, desolventizing, and refining to obtain 21.3g of a white cyanoolefine acid product.
Preparation of decarboxylated intermediates
Placing 10g of cyanoolefine acid into a high-pressure kettle, adding 100ml of dioxane and a catalytic amount of concentrated sulfuric acid, starting stirring, rotating at 180 r/min, carrying out decarboxylation reaction at 100 ℃, monitoring the reaction process by TLC, cooling to room temperature after 3h, separating the catalyst, and directly using the crude product in the next step.
Preparation of 11-aminoundecanoic acid
Adding 5 wt% of Raney nickel catalyst (ZL-N211 type, Zhongshan city catalyst factory) into the decarboxylated reaction system, closing the reaction kettle, sequentially replacing with nitrogen and hydrogen, keeping the hydrogen partial pressure of the system at 3Mpa, starting stirring, performing 180 revolutions per minute, heating the program to 100 ℃, reacting for 5 hours, then cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling dioxane under reduced pressure, washing and refining a crude product with water to obtain 6.3g of 11-aminoundecanoic acid, wherein the product is white powder, the purity is 98.0%, and the melting point is 190 ℃ (lit.).
Example 4
Preparation of methyl 9-oxononanoate
Putting 9-hydroxy nonanoic acid methyl ester (37.6g, 0.2mol) and CuO (17.5g, 0.2mol) into a reaction kettle, adding 200ml of tetrahydrofuran, starting stirring, rotating at 180 r/min, monitoring the reaction progress in real time, cooling to room temperature after 10h, filtering, distilling off the solvent under reduced pressure, and refining to obtain 31.9g of an off-white solid product (m/z: 186).
Preparation of cyanoolefine acid
Putting methyl 9-oxo-nonanoate (18.6g, 0.1mol), methyl cyanoacetate (9.9g, 0.1mol) and piperidine (4.3g, 50.0mmol) into a reaction kettle, adding 100ml dioxane as a solvent, starting stirring, rotating at 160 r/min, monitoring the reaction progress in real time at 50 ℃, cooling to room temperature after 10h, adding 80ml 10 wt% sodium hydroxide aqueous solution for hydrolysis, acidifying with 1N hydrochloric acid, and refining to obtain 20.5g pale yellow cyanoolefine acid product.
Preparation of decarboxylated intermediates
10g of cyanoolefine acid is put into an autoclave, 100ml of dioxane is added, stirring is started, 180 r/min is carried out, the temperature is 100 ℃, decarboxylation reaction is carried out, the reaction process is monitored by TLC, the temperature is reduced to room temperature after 5h, and the crude product is directly used for the next step.
Preparation of 11-aminoundecanoic acid
Adding 1 wt% of Pd/C catalyst (Pd content is 10%, Shanghai Kai New Material science and technology Co., Ltd.) into the decarboxylated reaction system, closing the reaction kettle, sequentially replacing with nitrogen and hydrogen, keeping the system at 2Mpa of hydrogen partial pressure, starting stirring, 180 r/min, heating to 100 ℃ to react for 3h, then cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling out dioxane under reduced pressure, washing and refining the crude product with water to obtain 5.9g of 11-aminoundecanoic acid, wherein the product is white powder, the purity is 99.2%, the melting point is 189 ℃ (lit.), (m/z: 201).
Example 5
Preparation of methyl 9-oxononanoate
Mixing methyl 9-hydroxynonanoate (37.6g, 0.2mol) with MnO2(17.4g, 0.2mol) is put into a reaction kettle, 200ml of tetrahydrofuran is added, stirring is started, 180 r/min is carried out, the temperature is 50 ℃, the reaction progress is monitored in real time, the temperature is reduced to room temperature after 8h, filtration is carried out, the solvent is distilled out under reduced pressure, and 34.4g of off-white solid product (m/z: 186) is obtained after refining treatment.
Preparation of cyanoolefine acid
Putting methyl 9-oxo-nonanoate (18.6g, 0.1mol), methyl cyanoacetate (9.9g, 0.1mol) and N, N-Diisopropylethylamine (DIPEA) (3.2g, 25.0mmol) into a reaction kettle, adding 100ml dioxane, starting stirring, stirring at 180 rpm and 50 ℃, monitoring the reaction process in real time, cooling to room temperature after 12h, adding 80ml 10 wt% NaOH aqueous solution for hydrolysis, acidifying with 1N hydrochloric acid, and refining to obtain 21.3g pale yellow cyano olefine acid product.
Preparation of decarboxylated intermediates
10g of cyanoolefine acid is put into an autoclave, 100ml of dioxane is added, stirring is started, 180 r/min is carried out, the temperature is 100 ℃, decarboxylation reaction is carried out, the reaction process is monitored by TLC, the temperature is reduced to room temperature after 5h, and the crude product is directly used for the next step.
Preparation of 11-aminoundecanoic acid
Adding 0.5 wt% of Pd/C catalyst (the Pd content is 10%, Shanghai Xuan New Material science and technology Co., Ltd.) into the decarboxylated reaction system, closing the reaction kettle, sequentially replacing with nitrogen and hydrogen, keeping the hydrogen partial pressure of the system at 3Mpa, starting stirring, rotating at 180 rpm, heating the program to 100 ℃, reacting for 1h, cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling under reduced pressure to obtain dioxane, washing and refining the crude product with water to obtain 4.9g of 11-aminoundecanoic acid, wherein the product is white powder, the purity is 98.1%, the melting point is 189 ℃ (lit.), (m/z: 201).
Example 6
Preparation of methyl 9-oxononanoate
9-hydroxy nonanoic acid methyl ester (37.6g, 0.2mol) and CuO (17.5g, 0.2mol) are placed in a reaction kettle, 200ml of dioxane is added, stirring is started, 180 r/min is carried out, the temperature is 25 ℃, the reaction process is monitored in real time, the temperature is reduced to room temperature after 10h, filtration is carried out, the solvent is distilled out under reduced pressure, and 30.2g of white-like solid product (m/z: 186) is obtained after refining treatment.
Preparation of cyanoolefine acid
Methyl 9-oxononanoate (18.6g, 0.1mol), methyl cyanoacetate (9.9g, 0.1mol) and Tetramethylethylenediamine (TMEDA) (2.3g, 20.0mmol) were placed in a reaction vessel, 100ml dioxane was added, stirring was started, the temperature was 180 rpm, the reaction progress was monitored in real time at 50 ℃, after 12h the temperature was lowered to room temperature, 80ml of 10 wt% NaOH aqueous solution was added for hydrolysis, 1N hydrochloric acid was acidified, and after purification 20.8g of a yellow cyanoacrylic acid product was obtained.
Preparation of decarboxylated intermediates
10g of cyanoolefine acid is put into an autoclave, 100ml of dioxane is added, stirring is started, 180 r/min is carried out, the temperature is 100 ℃, decarboxylation reaction is carried out, the reaction process is monitored by TLC, the temperature is reduced to room temperature after 5h, and the crude product is directly used for the next step.
Preparation of 11-aminoundecanoic acid
Adding 1 wt% of Raney nickel catalyst (ZL-N211 type, Zhongshan city catalyst factory) into the decarboxylated reaction system, closing the reaction kettle, sequentially replacing with nitrogen and hydrogen, keeping the hydrogen partial pressure of the system at 3Mpa, starting stirring, performing 180 revolutions per minute, heating the program to 100 ℃, reacting for 5 hours, then cooling to room temperature, slowly releasing pressure, filtering the reaction solution to remove the catalyst, distilling dioxane under reduced pressure, washing and refining a crude product with water to obtain 5.7g of 11-aminoundecanoic acid, wherein the product is white powder, the purity is 99.1%, and the melting point is 190 ℃ (lit.).
The types and equivalents of catalysts used in the knoevenagel condensation reactions in examples 1 to 6, the yields are summarized in table 1 below.
Table 1: effect of the amount of condensation catalyst on the reaction
The yields stated in table 1 are only those of the condensation step.
As described above, the invention provides a preparation method of 11-aminoundecanoic acid, which has the characteristics of mild reaction conditions, low cost, simplicity, easy operation and the like, and has wider application prospect and industrial production potential compared with the prior art.
Claims (10)
1. A method for preparing 11-aminoundecanoic acid, comprising the steps of:
1) dissolving the compound 9-hydroxy nonanoic acid or 9-hydroxy nonanoate in a solvent, and selectively oxidizing under the action of an oxidant to prepare the compound 9-oxo nonanoic acid or 9-oxo nonanoate in the formula II;
2) dissolving the 9-oxo-nonanoic acid or 9-oxo-nonanoate and cyanoacetate in a solvent, and carrying out knoevenagel condensation reaction under the action of a catalyst to obtain a compound shown in a formula III;
3) carrying out hydrolysis reaction on the compound of the formula III obtained in the step 2) under the action of a basic catalyst, and adding acid for acidification after the hydrolysis reaction is finished to obtain a compound of a formula IV, namely 2-cyanoundecane-2-enedioic acid;
4) carrying out selective decarboxylation reaction on the 2-cyano-undec-2-enedioic acid obtained in the step 3) to obtain a compound 10-cyano-10-ene decanoic acid shown in the formula V;
5) adding raney nickel or palladium carbon as a hydrogenation reduction reaction catalyst into the 10-cyano-10-ene decanoic acid obtained in the step 4), replacing the catalyst by nitrogen and hydrogen in sequence, carrying out hydrogenation reduction reaction to obtain a compound 11-aminoundecanoic acid shown in the formula VI,
wherein R is1Is H, or straight or branched C1-C10Alkyl, and R2Is straight-chain or branched C1-C10An alkyl group.
2. The method of claim 1, wherein R1Is H, or straight or branched C1-C6An alkyl group.
3. The preparation method according to claim 1, wherein the catalyst of knoevenagel condensation reaction is selected from one or more of triethylamine, N-diisopropylethylamine, N-methylmorpholine, tetramethylethylenediamine, piperidine, potassium hydroxide and sodium hydroxide.
4. The method of claim 1, wherein R2Is straight-chain or branched C1-C6An alkyl group.
5. The preparation method according to claim 1, wherein the solvent of the knoevenagel condensation reaction is selected from one or more of dioxane, ethyl acetate, tetrahydrofuran and N, N-dimethylformamide.
6. The production method according to any one of claims 1 to 5,
in step 1):
the oxidant is manganese dioxide, copper oxide or zinc oxide; the molar ratio of the oxidant to the 9-hydroxynonanoic acid or the 9-hydroxynonanoate is 1.0-2.0;
in step 2):
the molar ratio of the catalyst for the knoevenagel condensation reaction to 9-oxo-nonanoic acid or 9-oxo-nonanoate is 0.1-3.0;
the molar ratio of the 9-oxo-nonanoic acid or the 9-oxo-nonanoate to the cyanoacetate is 0.8-1.5: 1.0;
in step 3):
the alkaline catalyst for the hydrolysis reaction is an aqueous solution of lithium hydroxide, sodium hydroxide or potassium hydroxide, and the dosage of the catalyst is that the molar ratio of the catalyst to 9-oxo-nonanoic acid or 9-oxo-nonanoate is 1.0-2.5: 1.0;
in step 4):
the selective decarboxylation of the 2-cyanoundec-2-enedioic acid is carried out with or without a catalyst, wherein the catalyst is concentrated sulfuric acid or alkali;
in step 5):
the mass ratio of the dosage of the hydrogenation reduction reaction catalyst to the 2-cyano-undec-2-enedioic acid is 0.001-0.1.
7. The production method according to claim 6, wherein, in step 4), the base is sodium hydroxide, lithium hydroxide, or potassium hydroxide.
8. The production method according to any one of claims 1 to 5, wherein in step 5), the hydrogen partial pressure of the system for the hydrogenation reduction reaction is maintained at 1.0 to 6.0 MPa.
9. The production method according to any one of claims 1 to 5, wherein, in step 1), the molar ratio of the oxidizing agent to 9-hydroxynonanoic acid or 9-hydroxynonanoate is 1.0 to 1.2.
10. The production method according to any one of claims 1 to 5, wherein, in step 5), the mass ratio of the amount of the hydrogenation reduction reaction catalyst to 2-cyanoundec-2-enedioic acid is 0.001 to 0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710924314.4A CN109593045B (en) | 2017-09-30 | 2017-09-30 | Preparation method of 11-aminoundecanoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710924314.4A CN109593045B (en) | 2017-09-30 | 2017-09-30 | Preparation method of 11-aminoundecanoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109593045A CN109593045A (en) | 2019-04-09 |
| CN109593045B true CN109593045B (en) | 2021-10-01 |
Family
ID=65956434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710924314.4A Active CN109593045B (en) | 2017-09-30 | 2017-09-30 | Preparation method of 11-aminoundecanoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109593045B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539095A (en) * | 2020-11-26 | 2022-05-27 | 乐凯化学材料有限公司 | Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate |
| CN115448850B (en) * | 2022-09-19 | 2024-06-18 | 中国五环工程有限公司 | Process system and method for preparing 11-aminoundecanoic acid from 11-bromoundecanoic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009369A1 (en) * | 1978-09-15 | 1980-04-02 | Allied Corporation | Preparation of muconic acid mononitriles and copper(II)-ammonia reagent therefor |
| CN101663264A (en) * | 2007-02-15 | 2010-03-03 | 阿肯马法国公司 | Method for the synthesis of omega-amino-alkanoic acids |
| CN104968642A (en) * | 2013-02-08 | 2015-10-07 | 阿肯马法国公司 | Method of synthesising amino acid by metathesis, hydrolysis, then hydrogenation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2797983A2 (en) * | 2012-03-13 | 2014-11-05 | Invista Technologies S.à.r.l. | Nylon polymer and process |
-
2017
- 2017-09-30 CN CN201710924314.4A patent/CN109593045B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009369A1 (en) * | 1978-09-15 | 1980-04-02 | Allied Corporation | Preparation of muconic acid mononitriles and copper(II)-ammonia reagent therefor |
| CN101663264A (en) * | 2007-02-15 | 2010-03-03 | 阿肯马法国公司 | Method for the synthesis of omega-amino-alkanoic acids |
| CN104968642A (en) * | 2013-02-08 | 2015-10-07 | 阿肯马法国公司 | Method of synthesising amino acid by metathesis, hydrolysis, then hydrogenation |
Non-Patent Citations (3)
| Title |
|---|
| 1-Nonene-1,9-dicarboxylic acid;Bergmann, Felix;《Journal of the American Chemical Society》;19401231;第62卷;第3255页 * |
| Identification of Novel Triazole-Based Nicotinamide Phosphoribosyltransferase (NAMPT) Inhibitors Endowed with Antiproliferative and Antiinflammatory Activity;Cristina Travelli等;《J.Med.Chem.》;20170206;第60卷;第1768-1792页 * |
| Renewable materials as precursors of linear nitrile-acid derivatives via cross-metathesis of fatty esters and acids with acrylonitrile and fumaronitrile;Raluca Malacea等;《Green Chem.》;20091231;第11卷;第152-155页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109593045A (en) | 2019-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111187153B (en) | Preparation method of 1, 3-cyclohexanedione | |
| CN111662185B (en) | Synthesis method of N-methyl o-fluoroaniline | |
| CN109593045B (en) | Preparation method of 11-aminoundecanoic acid | |
| CN109369545B (en) | Synthesis process of 2-methyl-5-pyrazine formate | |
| CN110156620A (en) | A kind of preparation method of tranexamic acid | |
| CN101565400B (en) | Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid | |
| CN103724167B (en) | Environment-friendly synthesis method of high-yield perfluoromethylvinyl ether (PMVE) | |
| CN112062671A (en) | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid | |
| CN104710402A (en) | Dicyclohexyl crown ether synthesis method | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| CN111807968B (en) | Synthetic method of 2- (1-cyclohexenyl) ethylamine | |
| CN113773182A (en) | Method for synthesizing 6, 8-dichloro caprylic acid ester | |
| CN102173993B (en) | Method for synthesizing 4,6-diamino resorcinol dihydrochloride (DAR) | |
| CN103772151B (en) | A kind of preparation method of 2-methyl-3-phenyl benzil alcohol | |
| CN101475477A (en) | Preparation method of dimethyl fumarate | |
| CN109575036B (en) | Metal hematoporphyrin diether diester compound, catalyst and preparation method thereof, and cyclohexane catalytic oxidation method | |
| CN113402358A (en) | Novel synthesis method of cyclopropyl bromide | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| CN110713442A (en) | Preparation method of o-nitrobenzaldehyde | |
| CN114478315B (en) | Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst | |
| CN109134309B (en) | Method for purifying ethylene glycol bis (propionitrile) ether | |
| CN116082155B (en) | Method for preparing pinoxaden intermediate by using symmetrical epoxy compound | |
| CN100500643C (en) | Chemical synthesis of 3,4,5-trioxyaniline | |
| CN110092733B (en) | Preparation method of nonane dinitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |