Process for synthesizing alpha-chloro-alpha-acetyl-gamma-butyrolactone and co-producing methyl formate from aminopyrimidine mother liquor and application of process
By chlorinating the aminopyrimidine mother liquor with α-acetyl-γ-butyrolactone and synthesizing methyl formate using the aqueous layer, the problem of high cost of baking soda and formic acid in the prior art is solved, and the resource utilization and production costs are reduced.
Patent Information
- Application Number
- CN202411772309.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-04
- Publication Date
- 2025-03-04
AI Technical Summary
In the prior art, baking soda is consumed when chlorinated by α-acetyl-γ-butyrolactone, the cost of using formic acid in the esterification process is high, and the sodium formate in the aminopyrimidine mother liquor cannot be resource-based, resulting in higher production costs.
Under the condition of chlorine gas, the aminopyrimidine mother liquor was mixed with α-acetyl-γ-butyrolactone for chlorination to obtain α-chloro-α-acetyl-γ-butyrolactone and an aqueous layer, and methanol was added to the aqueous layer in a distillation device for esterification to synthesize methyl formate.
The use of baking soda and formic acid was eliminated, and the resource utilization of sodium formate in aminopyrimidine mother liquor was reduced, and the production cost was further reduced through co-production of methyl formate.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chlorination of α-acetyl-γ-butyrolactone, and in particular to a process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate and application thereof. Background Art
[0002] In the prior art, after 2-methyl-4-amino-5-formylaminomethylpyrimidine is hydrolyzed and separated from the product, the resulting aminopyrimidine mother liquor is directly processed in a triple-effect evaporator, resulting in the failure of sodium formate, a main substance contained in the mother liquor, to be recycled, resulting in a waste of sodium formate. Meanwhile, in the prior art, when α-acetyl-γ-butyrolactone is chlorinated, the alkaline substance consumed is baking soda, which has a high cost and is not conducive to reducing the production cost of the α-acetyl-γ-butyrolactone chlorination process. In addition, in the esterification synthesis process, formic acid and methanol are used for the esterification reaction, and the cost of the formic acid raw material is high, which is not conducive to reducing the production cost of the esterification process.
[0003] Therefore, in the above process, how to eliminate the use of baking soda and formic acid and realize the resource utilization of sodium formate in the aminopyrimidine mother liquor will effectively reduce the production cost of the process and improve the enterprise benefits.
[0004] In view of this, the present invention is proposed. Summary of the invention
[0005] One of the purposes of the present invention is to provide a process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from an aminopyrimidine mother liquor and co-producing methyl formate, which can solve the technical problems in the prior art that baking soda is consumed during the chlorination of α-acetyl-γ-butyrolactone, the cost of formic acid used in the esterification process is high, and the sodium formate contained in the aminopyrimidine mother liquor cannot be utilized as a resource.
[0006] The second object of the present invention is to provide an application of a process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from an aminopyrimidine mother liquor and co-producing methyl formate, which can avoid the use of relatively expensive raw materials such as baking soda and formic acid, and is conducive to significantly reducing production costs.
[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:
[0008] In a first aspect, a process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from an aminopyrimidine mother liquor and co-producing methyl formate comprises the following steps:
[0009] (a) under the condition of passing chlorine gas, the aminopyrimidine mother liquor and α-acetyl-γ-butyrolactone are mixed to carry out chlorination reaction, and then allowed to stand for stratification to obtain an α-chloro-α-acetyl-γ-butyrolactone layer and an aqueous layer;
[0010] The aminopyrimidine mother liquor is the mother liquor obtained after hydrolysis of 2-methyl-4-amino-5-formylaminomethylpyrimidine and separation of the product;
[0011] The aminopyrimidine mother solution contains sodium formate and water;
[0012] (b) adding methanol to the water layer of step (a) to carry out esterification reaction to obtain methyl formate.
[0013] Furthermore, the temperature of the chlorination reaction is 0°C-25°C.
[0014] Furthermore, the temperature of the chlorination reaction is 0°C-10°C.
[0015] Furthermore, the temperature of the chlorination reaction is 0°C-5°C.
[0016] Furthermore, the 2-methyl-4-amino-5-formylaminomethylpyrimidine is hydrolyzed by sodium hydroxide.
[0017] Furthermore, in the aminopyrimidine mother liquor, the mass proportion of sodium formate is 35%-45%, and the mass proportion of water is 65%-55%.
[0018] Further, step (b) comprises the following steps:
[0019] In the distillation device, methanol is added to the water layer to carry out esterification reaction and distillation to obtain methyl formate.
[0020] Furthermore, the top temperature of the distillation device is below 33°C.
[0021] Furthermore, the residual liquid of the distillation enters a three-effect system for evaporation and salt removal.
[0022] In a second aspect, a process as described in any one of the above is used for preparing α-chloro-α-acetyl-γ-butyrolactone or methyl formate.
[0023] Compared with the prior art, the present invention has at least the following beneficial effects:
[0024] The process for synthesizing α-chloro-α-acetyl-γ-butyrolactone and co-producing methyl formate from an aminopyrimidine mother liquor provided by the present invention comprises the following steps: coupling the aminopyrimidine mother liquor with α-acetyl-γ-butyrolactone for chlorination reaction, and utilizing the obtained water layer for esterification to synthesize methyl formate, thereby eliminating the use of relatively expensive intermediate raw materials such as baking soda and formic acid, and utilizing the sodium formate contained in the aminopyrimidine mother liquor in a resource-based manner; further utilizing the by-product formic acid to co-produce the synthesized methyl formate, thereby turning waste into treasure and reducing production costs; in short, the present invention solves the technical problems in the prior art that baking soda is consumed during the chlorination of α-acetyl-γ-butyrolactone, the formic acid used in the esterification process is relatively costly, and the sodium formate in the aminopyrimidine mother liquor cannot be utilized as a resource, thereby significantly reducing production costs.
[0025] The application of the process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate provided by the present invention can avoid the use of relatively expensive raw materials such as baking soda and formic acid, which is beneficial to significantly reduce production costs. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0027] Figure 1 A schematic diagram of a reaction for hydrolysis of 2-methyl-4-amino-5-formylaminomethylpyrimidine provided in one embodiment of the present invention;
[0028] Figure 2 A schematic diagram of a chlorination reaction of α-acetyl-γ-butyrolactone provided in one embodiment of the present invention;
[0029] Figure 3 A process flow chart for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate is provided in one embodiment of the present invention. DETAILED DESCRIPTION
[0030] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the 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.
[0031] According to a first aspect of the present invention, there is provided a process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from an aminopyrimidine mother liquor and co-producing methyl formate, comprising the following steps:
[0032] (a) under the condition of passing chlorine gas, the aminopyrimidine mother liquor and α-acetyl-γ-butyrolactone are mixed to carry out chlorination reaction, and then allowed to stand for stratification to obtain an α-chloro-α-acetyl-γ-butyrolactone layer and an aqueous layer;
[0033] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained after hydrolysis of 2-methyl-4-amino-5-formylaminomethylpyrimidine and separation of the product;
[0034] It should be noted that the hydrolysis of 2-methyl-4-amino-5-formylaminomethylpyrimidine can be carried out by hydrolysis with sodium hydroxide, see Figure 1 ;
[0035] The aminopyrimidine mother solution contains sodium formate and water;
[0036] (b) adding methanol to the water layer of step (a) to carry out esterification reaction to obtain methyl formate.
[0037] In the present invention, sodium formate in the aminopyrimidine mother liquor is used to replace the baking soda used in the chlorination of α-acetyl-γ-butyrolactone. Figure 2 The α-chloro-α-acetyl-γ-butyrolactone product obtained after chlorination is separated by the difference in specific gravity. The obtained lower layer is the α-chloro-α-acetyl-γ-butyrolactone layer, and the obtained upper layer is the water layer. Since the water layer contains by-product formic acid, methanol is introduced for esterification reaction, so that methyl formate can be synthesized in combination.
[0038] It can be seen that the present invention couples the aminopyrimidine mother liquor with α-acetyl-γ-butyrolactone to carry out chlorination reaction, and simultaneously utilizes the obtained water layer to esterify and synthesize methyl formate, thereby not only eliminating the use of relatively expensive intermediate raw materials such as baking soda and formic acid, but also reusing the sodium formate contained in the aminopyrimidine mother liquor, and utilizing the by-product formic acid to co-produce and synthesize methyl formate, thereby turning waste into treasure and reducing production costs.
[0039] In summary, the present invention solves the technical problems in the prior art that baking soda is consumed during the chlorination of α-acetyl-γ-butyrolactone, the cost of formic acid used in the esterification process is relatively high, and the sodium formate in the aminopyrimidine mother liquor cannot be recycled, which is conducive to significantly reducing production costs.
[0040] In the present invention, the mass proportion of sodium formate in the aminopyrimidine mother liquor can be 35%-45%, and its typical but non-limiting mass proportion is, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, and 45%; the mass proportion of water in the aminopyrimidine mother liquor can be 65%-55%, and its typical but non-limiting mass proportion is, for example, 65%, 64%, 63%, 62%, 61%, 60%, 59%, 58%, 57%, 56%, and 55%.
[0041] In a preferred embodiment, the temperature of the chlorination reaction can be 0°C-25°C, and typical but non-limiting temperatures are, for example, 0°C, 5°C, 10°C, 15°C, 20°C, and 25°C, which can ensure that the chlorination reaction proceeds fully and is conducive to improving the chlorination yield.
[0042] In a preferred embodiment, the temperature of the chlorination reaction may be 0°C-10°C, and may be further preferably 0°C-5°C, which is more conducive to further improving the chlorination yield.
[0043] In a preferred embodiment, step (b) of the present invention comprises the following steps:
[0044] In the distillation device, methanol is added to the water layer to carry out esterification reaction and distillation to obtain methyl formate.
[0045] In a preferred embodiment, the top temperature of the distillation unit may be below 33°C.
[0046] In the present invention, after methanol is added to the obtained water layer, the top temperature is controlled below 33° C. in the distillation device, so that methyl formate can be distilled, and the distillation residue containing water and sodium chloride can enter the triple-effect system for evaporation and salt removal.
[0047] A typical process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, the process is shown in Figure 3 , including the following steps:
[0048] (a) 240 g of α-acetyl-γ-butyrolactone was first added into a reaction device, and 318.75 g of aminopyrimidine mother liquor (the mother liquor had a sodium formate content of 40% and a water content of 60%) was added dropwise while chlorine was introduced, and the temperature was controlled to be 0° C.-25° C. to carry out chlorination reaction. After the reaction was completed, the reaction was allowed to stand for stratification, and the obtained lower layer was an α-chloro-α-acetyl-γ-butyrolactone layer, and the obtained upper layer was an aqueous layer, which contained sodium chloride and formic acid;
[0049] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained by hydrolyzing 2-methyl-4-amino-5-formylaminomethylpyrimidine with sodium hydroxide and separating the product;
[0050] (b) In a distillation apparatus, 66 g of methanol is added to the water layer for esterification reaction, and the top temperature of the tower is controlled below 33° C., thereby obtaining methyl formate by distillation, and the distillation residue containing water and sodium chloride enters a three-effect system for evaporation and salt removal.
[0051] According to a second aspect of the present invention, there is provided a use of any of the above-mentioned processes in the preparation of α-chloro-α-acetyl-γ-butyrolactone or methyl formate.
[0052] The application of the process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate provided by the present invention can avoid the use of relatively expensive raw materials such as baking soda and formic acid, which is beneficial to significantly reduce production costs.
[0053] The present invention is further described below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.
[0054] Example 1
[0055] A process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, the reaction process parameters and product yield are shown in Table 1, comprising the following steps:
[0056] (a) 240 g of α-acetyl-γ-butyrolactone was first added into a reaction device, and 318.75 g of aminopyrimidine mother liquor (the mother liquor had a sodium formate content of 40% and a water content of 60%) was added dropwise while chlorine was introduced, and the temperature was controlled to be 20° C.-25° C. to carry out chlorination reaction. After the reaction was completed, the mixture was allowed to stand for 6 h for stratification. The obtained lower layer was 298 g of α-chloro-α-acetyl-γ-butyrolactone layer (i.e., chlorination product), and the α-chloro-α-acetyl-γ-butyrolactone content was 95.1%. The chlorination reaction yield was 93%, and the obtained upper layer was an aqueous layer containing sodium chloride and formic acid;
[0057] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained by hydrolyzing 2-methyl-4-amino-5-formylaminomethylpyrimidine with sodium hydroxide and separating the product;
[0058] (b) In a distillation apparatus, 66 g of methanol was added to the water layer for esterification reaction, and the tower top temperature was controlled below 33° C., thereby obtaining 116.87 g of esterification product by distillation, with a methyl formate content of 94.4% and an esterification yield of 97.8%. The distillation residue containing water and sodium chloride entered a triple-effect system for evaporation and salt removal.
[0059] Example 2
[0060] A process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, the reaction process parameters and product yield are shown in Table 1, comprising the following steps:
[0061] (a) 240 g of α-acetyl-γ-butyrolactone was first added into a reaction device, and 318.75 g of aminopyrimidine mother liquor (the mother liquor had a sodium formate content of 40% and a water content of 60%) was added dropwise while chlorine was introduced, and the temperature was controlled to be 10° C.-15° C. for chlorination reaction. After the reaction was completed, the mixture was allowed to stand for 6 h for stratification. The obtained lower layer was 300 g of α-chloro-α-acetyl-γ-butyrolactone layer (i.e., chlorination product), and the α-chloro-α-acetyl-γ-butyrolactone content was 96.3%. The chlorination reaction yield was 94.8%, and the obtained upper layer was an aqueous layer containing sodium chloride and formic acid;
[0062] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained by hydrolyzing 2-methyl-4-amino-5-formylaminomethylpyrimidine with sodium hydroxide and separating the product;
[0063] (b) In a distillation apparatus, 66 g of methanol was added to the water layer for esterification reaction, and the tower top temperature was controlled below 33° C., thereby obtaining 114.1 g of esterification product by distillation, with a methyl formate content of 96.4% and an esterification yield of 97.7%. The distillation residue containing water and sodium chloride entered a triple-effect system for evaporation and salt removal.
[0064] Example 3
[0065] A process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, the reaction process parameters and product yield are shown in Table 1, comprising the following steps:
[0066] (a) 240 g of α-acetyl-γ-butyrolactone was first added into a reaction device, and 318.75 g of aminopyrimidine mother liquor (the mother liquor had a sodium formate content of 40% and a water content of 60%) was added dropwise while chlorine was introduced, and the temperature was controlled to be 5° C.-10° C. for chlorination reaction. After the reaction was completed, the mixture was allowed to stand for 6 h for stratification. The obtained lower layer was 304 g of α-chloro-α-acetyl-γ-butyrolactone layer (i.e., chlorination product), and the α-chloro-α-acetyl-γ-butyrolactone content was 98.3%. The chlorination reaction yield was 98.1%, and the obtained upper layer was an aqueous layer containing sodium chloride and formic acid;
[0067] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained by hydrolyzing 2-methyl-4-amino-5-formylaminomethylpyrimidine with sodium hydroxide and separating the product;
[0068] (b) In a distillation apparatus, 66 g of methanol was added to the water layer for esterification reaction, and the tower top temperature was controlled below 33° C., thereby obtaining 114.87 g of esterification product by distillation, with a methyl formate content of 96.2% and an esterification yield of 98.2%. The distillation residue containing water and sodium chloride entered a triple-effect system for evaporation and salt removal.
[0069] Example 4
[0070] A process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, the reaction process parameters and product yield are shown in Table 1, comprising the following steps:
[0071] (a) 240 g of α-acetyl-γ-butyrolactone was first added into a reaction device, and 318.75 g of aminopyrimidine mother liquor (the mother liquor had a sodium formate content of 40% and a water content of 60%) was added dropwise while chlorine was introduced, and the temperature was controlled to be 0° C.-5° C. for chlorination reaction. After the reaction was completed, the mixture was allowed to stand for 6 h for stratification. The obtained lower layer was 308 g of α-chloro-α-acetyl-γ-butyrolactone layer (i.e., chlorination product), and the α-chloro-α-acetyl-γ-butyrolactone content was 98.1%. The chlorination reaction yield was 99.1%, and the obtained upper layer was an aqueous layer containing sodium chloride and formic acid;
[0072] Wherein, the aminopyrimidine mother liquor is the mother liquor obtained by hydrolyzing 2-methyl-4-amino-5-formylaminomethylpyrimidine with sodium hydroxide and separating the product;
[0073] (b) In a distillation apparatus, 66 g of methanol was added to the water layer for esterification reaction, and the tower top temperature was controlled below 33° C., thereby obtaining 115.62 g of esterification product by distillation, with a methyl formate content of 95.2% and an esterification yield of 97.7%. The distillation residue containing water and sodium chloride entered a triple-effect system for evaporation and salt removal.
[0074] Table 1
[0075]
[0076] It can be seen that the present invention uses aminopyrimidine mother liquor and α-acetyl-γ-butyrolactone to carry out chlorination reaction, and uses the obtained water layer to esterify and synthesize methyl formate, which not only eliminates the use of relatively expensive intermediate raw materials such as baking soda and formic acid, but also makes resource utilization of sodium formate contained in the aminopyrimidine mother liquor, and also co-produces and synthesizes methyl formate, thereby greatly reducing the production cost.
[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A process for synthesizing α-chloro-α-acetyl-γ-butyrolactone from aminopyrimidine mother liquor and co-producing methyl formate, characterized in that: The following steps are involved: (a) under the condition of passing chlorine gas, the aminopyrimidine mother liquor and α-acetyl-γ-butyrolactone are mixed to carry out chlorination reaction, and then allowed to stand for stratification to obtain an α-chloro-α-acetyl-γ-butyrolactone layer and an aqueous layer; The aminopyrimidine mother liquor is the mother liquor obtained after hydrolysis of 2-methyl-4-amino-5-formylaminomethylpyrimidine and separation of the product; The aminopyrimidine mother solution contains sodium formate and water; (b) adding methanol to the water layer of step (a) to carry out esterification reaction to obtain methyl formate.
2. The process according to claim 1, characterized in that The temperature of the chlorination reaction is 0°C-25°C.
3. The process according to claim 2, characterized in that The temperature of the chlorination reaction is 0°C-10°C.
4. The process according to claim 3, characterized in that The temperature of the chlorination reaction is 0°C-5°C.
5. The process according to claim 1, characterized in that The 2-methyl-4-amino-5-formylaminomethylpyrimidine is hydrolyzed by sodium hydroxide.
6. The process according to any one of claims 1 to 5, characterized in that The mass proportion of sodium formate in the aminopyrimidine mother liquor is 35%-45%, and the mass proportion of water is 65%-55%.
7. The process according to claim 1, characterized in that Step (b) comprises the following steps: In the distillation device, methanol is added to the water layer to carry out esterification reaction and distillation to obtain methyl formate.
8. The process according to claim 7, characterized in that The top temperature of the distillation unit is below 33°C.
9. The process according to claim 7, characterized in that The residual liquid of the distillation enters the triple-effect system for evaporation and salt removal.
10. Use of the process according to any one of claims 1 to 9 in the preparation of α-chloro-α-acetyl-γ-butyrolactone or methyl formate.
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