Synthesis method of 3-(methyl hydroxyl phosphonyl) propionaldehyde
By adding boron-containing compounds as reaction accelerators to the glufosinate synthesis process, the problem of yield reduction caused by diethyl methyl phosphite hydrolysis is solved, and the effect of improving glufosinate yield and reducing production costs is achieved.
Patent Information
- Application Number
- CN202411417015.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2025-02-25
AI Technical Summary
In the existing glufosinate synthesis process, diethyl methyl phosphite is prone to hydrolysis, resulting in a decrease in yield, and its price is relatively expensive, which increases production costs.
During the addition reaction, a small amount of boron-containing compounds are added as the reaction accelerator to consume the water contained in acrolein, avoid the hydrolysis of diethyl methyl phosphite, and promote the addition reaction through the generated boric acid to improve the reaction yield.
It effectively avoids the hydrolysis loss of diethyl methyl phosphite, improves the yield and production efficiency of glufosinate, and reduces the overall production cost.
Smart Images
Figure BDA0005079721390000021 
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of pesticides, and in particular relates to a method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde. Background Art
[0002] Glufosinate is the second most widely used GM crop tolerant herbicide in the world after glyphosate and has been successfully commercialized. Glufosinate-tolerant crops include almost all major crops, and its market demand has greatly increased with the development of GM crops.
[0003] At present, there are many synthetic technology routes for glufosinate ammonium at home and abroad, among which the more mature process is the Streko-Zelinsky method. 3-(methylhydroxyphosphonyl) propionaldehyde is an important intermediate in the synthesis process, and is generally synthesized from diethyl methyl phosphite, acrolein and ethanol as raw materials. However, the moisture content in industrial acrolein is generally around 3%, and diethyl methyl phosphite is prone to hydrolysis, so a part of diethyl methyl phosphite will undergo hydrolysis reaction during the reaction, resulting in a decrease in yield. And because diethyl methyl phosphite is expensive, it accounts for a high proportion of the entire glufosinate raw material cost, which will further lead to an increase in the overall production cost. Therefore, it is necessary to find a method for synthesizing glufosinate ammonium that can effectively avoid the loss of diethyl methyl phosphite due to hydrolysis. Summary of the invention
[0004] In view of the above problems, the present invention provides a method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde.
[0005] To achieve the above purpose, the technical solution adopted by the present invention is:
[0006] A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde comprises dissolving a boron-containing compound in an alkyl alcohol, adding diethyl methylphosphite and acrolein to carry out an addition reaction, and then hydrolyzing the obtained intermediate to obtain the 3-(methylhydroxyphosphonyl)propionaldehyde.
[0007] Furthermore, the synthesis method comprises the following specific steps:
[0008] S1. Addition
[0009] The boron-containing compound is dissolved in an alkyl alcohol, and diethyl methyl phosphite and acrolein are added dropwise to carry out an addition reaction. After the reaction is completed, the solvent is removed by distillation under reduced pressure to obtain an intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane. The specific reaction equation is as follows:
[0010]
[0011] Wherein, R, R1, R2 and R3 are CH3 or C2H5 independently; R1, R2 and R3 can be derived from ROH or diethyl methyl phosphite;
[0012] S2. Hydrolysis
[0013] Acid and water are added to the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane to carry out a hydrolysis reaction. After the reaction is completed, distillation is performed under reduced pressure to obtain the 3-(methylhydroxyphosphonyl)propanal. The specific reaction equation is as follows:
[0014]
[0015] Wherein, R, R1, R2 and R3 are independently CH3 or C2H5 respectively; R1, R2 and R3 can be derived from ROH or diethyl methyl phosphite.
[0016] Furthermore, in step S2, the acid is sulfuric acid, hydrochloric acid, phosphoric acid or methanesulfonic acid.
[0017] Furthermore, the molar ratio of diethyl methylphosphite, acid and water is 1:0.01-0.05:10-15.
[0018] Furthermore, the boron-containing compound is boron oxide, trimethyl borate, triethyl borate, tripropyl borate or triisopropyl borate.
[0019] Furthermore, the amount of the boron-containing compound is 0.03 to 0.1 times the molar amount of acrolein.
[0020] Furthermore, the alkyl alcohol is methanol or ethanol.
[0021] Furthermore, the molar ratio of diethyl methyl phosphite to acrolein and alkyl alcohol is 1:1-1.05:2-6.
[0022] Furthermore, the temperature of the addition reaction is 30-45° C. and the time is 1-3 h.
[0023] Furthermore, the hydrolysis reaction temperature is 35-55° C. and the time is 1-3 h.
[0024] The beneficial effects of the synthesis method of 3-(methylhydroxyphosphonyl)propionaldehyde of the present invention are:
[0025] Since water is generated during the industrial production of acrolein, a small amount of water, generally about 3%, is contained in industrial acrolein products. However, diethyl methyl phosphite, a raw material for synthesizing 3-(methylhydroxyphosphonyl) propionaldehyde, is easily hydrolyzed to generate ethyl methyl phosphite, resulting in yield loss. Moreover, diethyl methyl phosphite is relatively expensive and accounts for a relatively high proportion of the total cost of glufosinate-ammonium raw materials. The present invention consumes the water contained in the acrolein raw material by adding a small amount of boron-containing compounds as reaction promoters during the addition reaction, thereby effectively avoiding the hydrolysis reaction of diethyl methyl phosphite. Moreover, the boron-containing compounds react with water to generate boric acid, which is a Lewis acid and has a promoting effect on the addition reaction, thereby further improving the reaction yield and reducing the production cost of glufosinate-ammonium.
[0026] The synthetic method of the invention is simple in overall operation and can be easily implemented in industrial production. DETAILED DESCRIPTION
[0027] The technical solutions in the embodiments of the present invention are described clearly and completely below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.
[0028] Example 1 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0029] S1. Addition
[0030] Add 2.88g (0.015mol, 98%) tripropyl borate to 46g (1mol) ethanol, and simultaneously add dropwise 69.4g (0.5mol, 98%) diethyl methyl phosphite and 28.6g (0.5mol, 98%) acrolein. Control the reaction temperature at 30°C. After the addition is complete, keep the temperature at 30°C for addition reaction for 3h. Then, evaporate the solvent under reduced pressure at 60°C to obtain the intermediate 1-diethoxy-3-(ethoxymethylphosphonyl)propane.
[0031] S2. Hydrolysis
[0032] Subsequently, 90 g (5 mol) of water and 2.35 g (0.02 mol, 31%) of hydrochloric acid were added to the intermediate 1-diethoxy-3-(ethoxymethylphosphonyl)propane, and the reaction was hydrolyzed at 35°C for 1 hour. After the hydrolysis reaction was completed, the reaction was distilled at 60°C under reduced pressure to obtain 67.3 g of 3-(methylhydroxyphosphonyl)propanal with a content of 98.2% and a yield of 97.2%.
[0033] The specific reaction equation is as follows:
[0034]
[0035] Among them, R, R1, R2 and R3 are all C2H5.
[0036] Example 2 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0037] S1. Addition
[0038] 5.87g (0.0306mol, 98%) of triisopropyl borate was added to 92g (2mol) of ethanol, and 69.4g (0.5mol, 98%) of diethyl methylphosphite and 29.1g (0.51mol, 98%) of acrolein were added dropwise at the same time, and the reaction temperature was controlled at 40°C. After the addition was completed, the addition reaction was carried out at 40°C for 2h, and the solvent was evaporated under reduced pressure at 60°C to obtain the intermediate 1-dialkoxy-3-(ethoxymethylphosphonyl)propane. In this embodiment, 1-diethoxy-3-(ethoxymethylphosphonyl)propane is 1-diethoxy-3-(ethoxymethylphosphonyl)propane.
[0039] S2. Hydrolysis
[0040] Subsequently, 135 g (7.5 mol) of water and 1.73 g (0.015 mol, 80%) of phosphoric acid were added to the intermediate 1-diethoxy-3-(ethoxymethylphosphonyl)propane, and the reaction was hydrolyzed at 50°C for 3 hours. After the hydrolysis reaction was completed, the reaction was distilled at 60°C under reduced pressure to obtain 67.6 g of 3-(methylhydroxyphosphonyl)propanal with a content of 98.1% and a yield of 97.5%.
[0041] The specific reaction equation is as follows:
[0042]
[0043] Among them, R, R1, R2 and R3 are all C2H5.
[0044] Example 3 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0045] S1. Addition
[0046] 2.71 g (0.0255 mol, 98%) of trimethyl borate was added to 96 g (3 mol) of methanol, and 69.4 g (0.5 mol, 98%) of diethyl methyl phosphite and 29.1 g (0.51 mol, 98%) of acrolein were added dropwise at the same time. The reaction temperature was controlled at 40°C. After the addition was completed, the addition reaction was carried out at 40°C for 1 hour. The solvent was evaporated at 60°C under reduced pressure to obtain the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane. In this embodiment, 1-dialkoxy-3-(alkoxymethylphosphonyl)propane is a mixture of 1-dimethoxy-3-(ethoxymethylphosphonyl)propane, 1-diethoxy-3-(ethoxymethylphosphonyl)propane, 1-methoxy-1-ethoxy-3-(ethoxymethylphosphonyl)propane, 1-dimethoxy-3-(methoxymethylphosphonyl)propane, 1-diethoxy-3-(methoxymethylphosphonyl)propane and 1-methoxy-1-ethoxy-3-(methoxymethylphosphonyl)propane.
[0047] S2. Hydrolysis
[0048] Subsequently, 90 g (5 mol) of water and 1.37 g (0.01 mol, 70%) of methanesulfonic acid were added to the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane, and the reaction was hydrolyzed at 55°C for 2 hours. After the hydrolysis reaction was completed, the reaction was distilled at 60°C under reduced pressure to obtain 67.9 g of 3-(methylhydroxyphosphonyl)propanal with a content of 98.1% and a yield of 98.0%.
[0049] The specific reaction equation is as follows:
[0050]
[0051] Wherein, R is CH3, R1 is CH3 or C2H5, R2 is CH3 or C2H5, R3 is CH3 or C2H5, and R1, R2 and R3 are independent of each other.
[0052] Example 4 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0053] S1. Addition
[0054] Add 3.75g (0.0525mol, 98%) boric oxide to 64g (2mol) methanol, and simultaneously add dropwise 69.4g (0.5mol, 98%) diethyl methyl phosphite and 30.0g (0.525mol, 98%) acrolein. Control the reaction temperature at 45°C. After the addition is complete, heat at 45°C for 2h to carry out the addition reaction. Then, evaporate the solvent under reduced pressure at 60°C to obtain the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane. In this embodiment, 1-dialkoxy-3-(alkoxymethylphosphonyl)propane is a mixture of 1-dimethoxy-3-(ethoxymethylphosphonyl)propane, 1-diethoxy-3-(ethoxymethylphosphonyl)propane, 1-methoxy-1-ethoxy-3-(ethoxymethylphosphonyl)propane, 1-dimethoxy-3-(methoxymethylphosphonyl)propane, 1-diethoxy-3-(methoxymethylphosphonyl)propane and 1-methoxy-1-ethoxy-3-(methoxymethylphosphonyl)propane.
[0055] S2. Hydrolysis
[0056] Subsequently, 108 g (6 mol) of water and 0.53 g (0.005 mol, 92%) of sulfuric acid were added to the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane, and the reaction was hydrolyzed at 50°C for 1.5 h. After the hydrolysis reaction was completed, the reaction was distilled at 60°C under reduced pressure to obtain 67.7 g of 3-(methylhydroxyphosphonyl)propanal with a content of 98.3% and a yield of 97.9%.
[0057] The specific reaction equation is as follows:
[0058]
[0059] Wherein, R is CH3, R1 is CH3 or C2H5, R2 is CH3 or C2H5, R3 is CH3 or C2H5, and R1, R2 and R3 are independent of each other.
[0060] Example 5 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0061] S1. Addition
[0062] 3.13 g (0.021 mol, 98%) of triethyl borate was added to 64 g (2 mol) of methanol, and 69.4 g (0.5 mol, 98%) of diethyl methyl phosphite and 30.0 g (0.525 mol, 98%) of acrolein were added dropwise at the same time. The reaction temperature was controlled at 45°C. After the addition was completed, the addition reaction was carried out at 45°C for 1 hour. The solvent was evaporated under reduced pressure at 60°C to obtain the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane. In this embodiment, 1-dialkoxy-3-(alkoxymethylphosphonyl)propane is a mixture of 1-dimethoxy-3-(ethoxymethylphosphonyl)propane, 1-diethoxy-3-(ethoxymethylphosphonyl)propane, 1-methoxy-1-ethoxy-3-(ethoxymethylphosphonyl)propane, 1-dimethoxy-3-(methoxymethylphosphonyl)propane, 1-diethoxy-3-(methoxymethylphosphonyl)propane and 1-methoxy-1-ethoxy-3-(methoxymethylphosphonyl)propane.
[0063] S2. Hydrolysis
[0064] Subsequently, 108 g (6 mol) of water and 3.43 g (0.025 mol, 70%) of methanesulfonic acid were added to the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane, and the reaction was hydrolyzed at 55°C for 1 hour. After the hydrolysis reaction was completed, the reaction was distilled at 60°C under reduced pressure to obtain 67.5 g of 3-(methylhydroxyphosphonyl)propanal with a content of 98.5% and a yield of 97.8%.
[0065] The specific reaction equation is as follows:
[0066]
[0067] Wherein, R is CH3, R1 is CH3 or C2H5, R2 is CH3 or C2H5, R3 is CH3 or C2H5, and R1, R2 and R3 are independent of each other.
[0068] Comparative Example 1 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0069] This comparative example is a comparative test of the synthesis process of 3-(methylhydroxyphosphonyl)propionaldehyde in Example 3, which is basically the same as the operating steps and process parameters in Example 3, except that trimethyl borate is not added in step S1 (that is, except for not adding trimethyl borate, other condition parameters are exactly the same as those in Example 3), and finally 66.1g of the product 3-(methylhydroxyphosphonyl)propionaldehyde is obtained, with a content of 96.4% and a yield of 93.7%.
[0070] Comparative Example 2 A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde
[0071] This comparative example is a comparative test of the synthesis process of 3-(methylhydroxyphosphonyl)propionaldehyde in Example 5, which is basically the same as the operating steps and process parameters in Example 5, except that triethyl borate is not added in step S1 (that is, except for not adding triethyl borate, other conditions are exactly the same as in Example 5), and finally 66.7 g of the product 3-(methylhydroxyphosphonyl)propionaldehyde is obtained, with a content of 96.0% and a yield of 94.1%.
[0072] By comparing Example 3 with Comparative Example 1 and Example 5 with Comparative Example 2, it can be seen that the present invention can significantly improve the content (i.e., purity) and yield of the prepared product 3-(methylhydroxyphosphonyl)propionaldehyde by adding a boron-containing compound as a reaction accelerator.
[0073] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
Claims
1. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde, characterized in that: The synthesis method comprises dissolving a boron-containing compound in an alkyl alcohol, adding diethyl methylphosphite and acrolein to carry out an addition reaction, and then subjecting the obtained intermediate to a hydrolysis reaction to obtain the 3-(methylhydroxyphosphonyl) propionaldehyde.
2. The method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to claim 1, characterized in that: The synthesis method comprises the following specific steps: S1. Addition The boron-containing compound is dissolved in an alkyl alcohol, and diethyl methyl phosphite and acrolein are added dropwise to carry out an addition reaction to obtain an intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane; S2. Hydrolysis Acid and water are added to the intermediate 1-dialkoxy-3-(alkoxymethylphosphonyl)propane to carry out a hydrolysis reaction to obtain the 3-(methylhydroxyphosphonyl)propanal.
3. The method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to claim 2, characterized in that: In step S2, the acid is sulfuric acid, hydrochloric acid, phosphoric acid or methanesulfonic acid.
4. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to claim 2 or 3, characterized in that: The molar ratio of diethyl methylphosphite, acid and water is 1:0.01-0.05:10-15.
5. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The boron-containing compound is boron oxide, trimethyl borate, triethyl borate, tripropyl borate or triisopropyl borate.
6. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The amount of the boron-containing compound used is 0.03 to 0.1 times the molar amount of acrolein.
7. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The alkyl alcohol is methanol or ethanol.
8. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The molar ratio of diethyl methyl phosphite, acrolein and alkyl alcohol is 1:1-1.05:2-6.
9. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The temperature of the addition reaction is 30-45°C and the time is 1-3h.
10. A method for synthesizing 3-(methylhydroxyphosphonyl)propionaldehyde according to any one of claims 1 to 3, characterized in that: The temperature of the hydrolysis reaction is 35-55°C and the time is 1-3h.