CN117865844A - Continuous synthesis method of ethyl benzaminoacetate - Google Patents
Continuous synthesis method of ethyl benzaminoacetate Download PDFInfo
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- CN117865844A CN117865844A CN202311633363.4A CN202311633363A CN117865844A CN 117865844 A CN117865844 A CN 117865844A CN 202311633363 A CN202311633363 A CN 202311633363A CN 117865844 A CN117865844 A CN 117865844A
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- continuous flow
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- 238000001308 synthesis method Methods 0.000 title abstract description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- TXTWXQXDMWILOF-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)azanium;chloride Chemical compound [Cl-].CCOC(=O)C[NH3+] TXTWXQXDMWILOF-UHFFFAOYSA-N 0.000 claims abstract description 17
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- -1 ethyl benzylidene amino Chemical group 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 2
- 229910000856 hastalloy Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 7
- 229930182817 methionine Natural products 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a continuous synthesis method of ethyl benzaminoacetate. The continuous flow synthesis method can realize the accurate control of reaction conditions and improve the selectivity and purity of the product. In addition, the continuous flow synthesis method enables reactants to be fed at a proper rate, avoids severe reaction under high concentration, and improves the safety of production reaction. Through designing and constructing a continuous flow micro-reaction module, dissolving glycine ethyl ester hydrochloride and a catalyst triethylamine in toluene under the nitrogen atmosphere to obtain a homogeneous material A; the other reactant benzaldehyde is a material B. The feed rate of A was adjusted to 36.96ml/min by adjusting the liquid flow meter and feed rate of B was controlled to 4.41ml/min by the liquid plunger pump. The material A and the material B flow into a product storage tank after being introduced into a micro-reaction module to carry out continuous synthesis reaction.
Description
Technical Field
The invention relates to a continuous synthesis method of ethyl phenylmethyleneamino acetate, in particular to the technical field of preparation of methionine intermediates by using continuous flow equipment.
Background
Methionine is also known as methionine and has the molecular formula C 5 H 11 NO 2 S, the appearance is white flaky crystals or powder, and the product has special smell and slightly sweet taste. Methionine is one of the basic units constituting proteins, is the only sulfur-containing amino acid among amino acids required for animal growth, and is widely used in the fields of medical nutrition, food-grade additives, feed additives, and the like.
In recent years, as protein feed resources are becoming scarce, the addition of specific essential amino acids to feeds has become increasingly common. At present, methionine is in short supply in the market of China, wherein ethyl benzaminoacetate is an important intermediate for synthesizing green methionine.
The intermittent synthesis method of the intermediate ethyl benzylidene amino acetate of methionine has complicated operation and low yield. Thus, there is a need for an improved process for the preparation of ethyl benzaminoacetate.
Disclosure of Invention
Therefore, the invention aims to provide a continuous synthesis method of ethyl benzaminoacetate, which solves the problems of complex operation, improved raw material utilization rate, shortened reaction time and low yield of the existing synthesis method.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
a method for synthesizing continuous ethyl benzylidene amino acetate, comprising the steps of:
s1: dissolving glycine ethyl ester hydrochloride and a catalyst triethylamine in toluene serving as a solvent, and uniformly mixing in a stirring device to obtain a homogeneous material A; the reactant benzaldehyde is a material B;
s2: and the material A is metered by a liquid plunger pump and the material B by a liquid flowmeter and then is fed into a continuous flow micro-reaction device respectively to synthesize the ethyl phenylmethyleneamino acetate.
Preferably, in the synthesis method S1, glycine ethyl ester hydrochloride: triethylamine: the molar ratio of benzaldehyde is 1: (0.7-1): (1 to 1.5), particularly preferably 1: (0.7-1): (1-1.2).
Preferably, in the synthesis method S1, the process pressure in the continuous flow micro-reactor 1 is normal pressure, the feeding flow of the material a is 5-40 ml/min, the feeding flow of the material B is 0.5-5 ml/min, the residence time of the materials a and B in the continuous flow micro-reactor is 1-5 min, and the control temperature of the reactor is 80-120 ℃.
Preferably, in the synthesis method S1, the triethylamine is used as a base catalyst, and the pH is in the range of 7 to 12, particularly preferably in the range of 7 to 10.
Preferably, in the synthesis method S1, the organic solvent is one of toluene, dichloroethane and tetrahydrofuran, and toluene is particularly preferred.
Preferably, in the synthesis method S1, the method for preparing ethyl benzaminoacetate by using a continuous flow micro-reaction device is characterized in that: the weight ratio of glycine ethyl ester hydrochloride to toluene in the solution A is 1:1-10.
The continuous flow reactor or the tubular reactor; the material is silicon carbide, hastelloy, glass, 304 or 316, etc.; the feeding pump is a liquid plunger pump; the stirring kettle is magnetically stirred.
The beneficial effects are that: the invention synthesizes the ethyl phenylmethyleneamino acetate by adopting a continuous flow microreactor device, the reaction temperature is 80-120 ℃, the reaction time is 1-5 min, the yield reaches 89.5%, and the purity reaches 90.3%. The continuous flow micro-reactor method has the characteristics of short reaction time, simple operation, high efficiency and safety, and provides a basis for industrial amplification.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention clearer, the present invention provides the following drawings:
FIG. 1 is a schematic flow chart of a continuous process for synthesizing ethyl benzylidene amino acetate.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings, but the scope of the patent claims is not limited to the scope of the examples.
A continuous synthesis method of ethyl benzaminoacetate comprises the following steps:
example 1
(1) 69.79g (0.5 mol) of glycine ethyl ester hydrochloride and 50.595g (0.5 mol) of triethylamine were weighed out and dissolved in 139.58g of toluene under nitrogen protection to give a material A. 37.14g (0.35 mol) of benzaldehyde is added as a material B, and the solution A and the solution B are connected with a feed inlet of a continuous flow micro-reaction device under the protection of nitrogen and are used as a reactant.
The flow rate of solution A was 36.96ml/min and the flow rate of solution B was 4.41ml/min. The reaction temperature of the continuous flow micro-reaction device is controlled to be 80-120 ℃ and the residence time is controlled to be 1min, the obtained reaction liquid C is continuously conveyed into a liquid storage tank, the yield of the product after post-treatment reaches 89.5%, and the purity reaches 90.3%.
In the batch kettle reaction, glycine ethyl ester hydrochloride and benzaldehyde are easy to generate byproducts due to the change of pH in the synthesis process, so that the yield of the benzaminoacetic acid ethyl ester is low, and the purity is poor; the continuous flow micro-reactor process can improve the yield and purity of the product.
Example 2
This example is identical to example 1, with the only difference that the residence time in this example is 5min. The flow rate of solution A was 7.40ml/min and the flow rate of solution B was 0.88ml/min. The reaction temperature of the continuous flow micro-reaction device is controlled to be 80-120 ℃ and the residence time is 5min, the obtained reaction liquid C is continuously conveyed into a liquid storage tank, the yield of the product after post-treatment reaches 88.1%, and the purity reaches 88.3%.
Example 3
This example is identical to example 1, with the only difference that the organic solvent in this example is tetrahydrofuran. 69.79g (0.5 mol) of glycine ethyl ester hydrochloride and 50.595g (0.5 mol) of triethylamine were weighed out and dissolved in 139.58g of tetrahydrofuran under the protection of nitrogen to give a material A. 37.14g (0.35 mol) of benzaldehyde is added as a material B, and the solution A and the solution B are connected with a feed inlet of a continuous flow micro-reaction device under the protection of nitrogen and are used as a reactant.
The flow rate of solution A was 36.96ml/min and the flow rate of solution B was 4.41ml/min. The reaction temperature of the continuous flow micro-reaction device is controlled to be 80-120 ℃ and the residence time is controlled to be 1min, the obtained reaction liquid C is continuously conveyed into a liquid storage tank, the yield of the product after post-treatment is 79.0%, and the purity is 88.2%.
Example 4
This example is identical to example 1, with the only difference that the organic solvent in this example is dichloroethane. 69.79g (0.5 mol) of glycine ethyl ester hydrochloride and 50.595g (0.5 mol) of triethylamine were weighed out and dissolved in 139.58g of dichloroethane under nitrogen protection as a material A. 37.14g (0.35 mol) of benzaldehyde is added as a material B, and the solution A and the solution B are connected with a feed inlet of a continuous flow micro-reaction device under the protection of nitrogen and are used as a reactant.
The flow rate of solution A was 36.96ml/min and the flow rate of solution B was 4.41ml/min. The reaction temperature of the continuous flow micro-reaction device is controlled to be 80-120 ℃ and the residence time is controlled to be 1min, the obtained reaction liquid C is continuously conveyed into a liquid storage tank, and the yield of the product after post-treatment is 89.0%, and the purity is 88.2%.
Comparative example 1
Dissolving glycine ethyl ester hydrochloride and triethylamine in toluene under the protection of nitrogen, adding benzaldehyde, wherein the feeding molar ratio of the glycine ethyl ester hydrochloride to the triethylamine is 1:1:0.7, finishing feeding in an oil bath, and then carrying out reflux reaction for 4 hours at 85-110 ℃; after the reaction, the mixture was concentrated, water and ethyl acetate were added to extract, and the extracted organic phase was washed with water, saturated brine, dried over anhydrous sodium sulfate, and the concentrated brown oil (ethyl benzaminoacetate) was filtered to give a yield of 80.0% and a purity of 77.0%.
Comparative example 2
Dissolving glycine ethyl ester hydrochloride, anhydrous sodium sulfate and benzaldehyde into tetrahydrofuran, slowly dropwise adding triethylamine under stirring, and reacting at room temperature for 24h, wherein the feeding molar ratio of glycine ethyl ester hydrochloride to benzaldehyde to triethylamine is 1:1:0.7. The mixture was filtered and the tetrahydrofuran was distilled off under reduced pressure to give a brown oil (ethyl benzaminoacetate) in a yield of 76.2% and a purity of 56.4%.
Comparative example 3
Dissolving glycine ethyl ester hydrochloride, anhydrous magnesium sulfate and benzaldehyde into dichloromethane, adding triethylamine under stirring, wherein the feeding molar ratio of the glycine ethyl ester hydrochloride to the benzaldehyde to the triethylamine is 1:1.2:1, finishing feeding in a water bath, and then reacting for 24 hours under a greenhouse; after the reaction was completed, the mixture was filtered, concentrated under reduced pressure and the methylene chloride was distilled off to obtain a brown oil (ethyl benzaminoacetate) having a yield of 80.1% and a purity of 64.3%.
Claims (7)
1. A continuous preparation method of ethyl benzylidene amino acetate is characterized by comprising the following steps of:
s1: dissolving glycine ethyl ester hydrochloride and a catalyst triethylamine in toluene serving as a solvent, and uniformly mixing in a stirring device to obtain a homogeneous material A; the reactant benzaldehyde is a material B;
s2: and the material A is metered by a liquid plunger pump and the material B by a liquid flowmeter and then is fed into a continuous flow microreactor respectively to synthesize the ethyl phenylmethyleneamino acetate.
2. The method according to claim 1, wherein in S1, glycine ethyl ester hydrochloride: triethylamine: the molar ratio of benzaldehyde is 1: (0.7-1): (1-1.5).
3. The preparation method according to claim 1, wherein in the step S1, the process pressure in the continuous flow micro-reactor is normal pressure, the feeding flow of the material a is 5-40 ml/min, the feeding flow of the material B is 0.5-5 ml/min, the residence time of the materials a and B in the continuous flow micro-reactor is 1-5 min, and the control temperature of the reactor is 80-120 ℃.
4. The process according to claim 1, wherein the triethylamine is used as a base catalyst and has a pH in the range of 7 to 12.
5. The preparation method according to claim 1, wherein the organic solvent is one of toluene, dichloroethane and tetrahydrofuran, preferably toluene.
6. The method of manufacturing according to claim 1, characterized in that: the weight ratio of glycine ethyl ester hydrochloride to toluene in the solution A is 1:1-10.
7. The method of claim 1, wherein the continuous flow reactor or the tubular reactor; the material is silicon carbide, hastelloy, glass, 304 or 316.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311633363.4A CN117865844A (en) | 2023-11-28 | 2023-11-28 | Continuous synthesis method of ethyl benzaminoacetate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311633363.4A CN117865844A (en) | 2023-11-28 | 2023-11-28 | Continuous synthesis method of ethyl benzaminoacetate |
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| CN117865844A true CN117865844A (en) | 2024-04-12 |
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- 2023-11-28 CN CN202311633363.4A patent/CN117865844A/en active Pending
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