CN113527105A - Preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene - Google Patents
Preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene Download PDFInfo
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- CN113527105A CN113527105A CN202110849087.XA CN202110849087A CN113527105A CN 113527105 A CN113527105 A CN 113527105A CN 202110849087 A CN202110849087 A CN 202110849087A CN 113527105 A CN113527105 A CN 113527105A
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Abstract
The invention discloses a preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, which comprises the following steps: dissolving trinitrophloroglucinol into an alkylating reagent with the mass 5 times that of the trinitrophloroglucinol to obtain a raw material solution; pumping the raw material liquid into a continuous flow tubular reactor I to react for 5-30min at the temperature of 80-110 ℃ to obtain alkylation reaction liquid; feeding the alkylation reaction liquid into a continuous flow tubular reactor II for cooling for 5-10min, wherein the cooling temperature is 20-30 ℃; and taking out the product, adding the product into a crystallization solution, cooling, crystallizing, stirring, filtering and drying to obtain the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the alkylating reagent is a methylating reagent, an ethylating reagent or a propylating reagent. The continuous flow technology is utilized to inhibit side reaction, improve the yield and purity of the target product and greatly simplify the post-treatment process. Easy to control the reaction process and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of fine chemical synthesis processes, and in particular relates to a preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene.
Background
1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene belongs to an important organic compound and can be used as an intermediate for synthesizing compounds such as TATB or the like.
At present, the preparation of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene is carried out in a kettle type reaction, but the kettle type reaction is not easy to control various parameters such as temperature, time and the like in the reaction process, so that the conditions of coking and carbonization are easy to occur, even the explosion risk is caused because the heat release cannot be timely discharged, a plurality of reaction byproducts are generated, the subsequent purification process is difficult and complicated, and the product purity is low. And the reaction time is longer, so that the method is not suitable for the timeliness of industrial production.
Based on this, the present patent is proposed.
Disclosure of Invention
The invention aims to solve the technical problems that the existing preparation process of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene is not easy to control, a plurality of byproducts are produced, and the reaction time is long, and aims to provide a preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene, which solves the problems that the existing preparation process of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene is not easy to control, a plurality of byproducts are produced, and the reaction time is long.
The invention is realized by the following technical scheme:
a preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene comprises the following steps:
(1) dissolving trinitrophloroglucinol into an alkylating reagent with the mass 5 times that of the trinitrophloroglucinol to obtain a raw material solution;
(2) pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I, and reacting for 5-30min at the temperature of 80-110 ℃ to obtain alkylation reaction liquid;
(3) feeding the alkylation reaction solution in the step (2) into a continuous flow tubular reactor II for cooling for 5-10min, wherein the circulating cooling temperature of the continuous flow tubular reactor II is 20-30 ℃;
(4) adding a product taken out from an outlet of the continuous flow tubular reactor II into a crystallization solution, cooling, crystallizing, stirring, filtering and drying to obtain a product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene;
the alkylating agent is a methylating agent or an ethylating agent or a propylating agent.
Preferably, the alkylating agent in step (1) is trimethyl orthoformate or dimethyl sulfate or triethyl orthoformate.
Preferably, the reaction temperature of the raw material liquid in the step (2) in the continuous flow tubular reactor I is 90-100 ℃, and the reaction time is 10-15 minutes.
Preferably, the crystallization solution in the step (4) is one or more of C1-C3 alcohols.
Preferably, the crystallization solution in step (4) is one or more of methanol, ethanol and isopropanol, and more preferably methanol.
Preferably, the weight ratio of the crystallization solution to the alkylating agent in the step (4) is 1: 1-10: 1, more preferably 3: 1.
preferably, the temperature of the cooling crystallization process in the step (4) is 5-10 ℃.
Preferably, the flow rate of the raw material liquid pumped into the continuous flow tubular reactor I in the step (1) is 10ml/min to 500ml/min, more preferably 50ml/min to 200 ml/min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the preparation method of the 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene, provided by the embodiment of the invention, the alkylation reaction is carried out by using a continuous flow technology, different reaction temperature zones are set, the reaction is started at a high temperature in a continuous flow tubular reactor I at a temperature of 80-110 ℃ to obtain the alkylation reaction liquid containing mononitro and dinitroated intermediate state, then the alkylation reaction liquid is fed into a continuous flow tubular reactor II at a low temperature zone, and the temperature is reduced to inhibit the intermediate state product from generating side reaction, so that the yield and the purity of the target product 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene are improved, and the treatment process after the reaction is greatly simplified. The yield of the obtained 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene is as high as 95 percent, and the purity is as high as 98 percent.
Meanwhile, the alkylation reagent after the reaction is finished is easy to recover, zero emission is realized, and the method is environment-friendly and pollution-free. The continuous flow tubular reactor is easy to control the temperature, time and other parameters in the reaction process, greatly shortens the reaction time and is suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
A preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of trimethyl orthoformate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulating temperature of the continuous flow tubular reactor I to be 100 ℃ and stable, and setting the circulating temperature of the continuous flow tubular reactor II to be 30 ℃ and stable; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 50.0ml/min, and reacting for 5min at the temperature of 100 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) adding a product containing 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene taken out from an outlet of a continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 110g of the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 95%, and the purity is 98% by HPLC detection.
Example 2
A preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of dimethyl sulfate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulating temperature of the continuous flow tubular reactor I to be 100 ℃ and stable, and setting the circulating temperature of the continuous flow tubular reactor II to be 30 ℃ and stable; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 50.0ml/min, and reacting for 5min at the temperature of 100 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) adding a product containing 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene taken out from an outlet of a continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 109g of the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 95%, and the purity is 98% by HPLC detection.
Example 3
A preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of trimethyl orthoformate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulating temperature of the continuous flow tubular reactor I to be 90 ℃ and reach stability, and setting the circulating temperature of the continuous flow tubular reactor II to be 30 ℃ and reach stability; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 50.0ml/min, and reacting for 5min at the temperature of 90 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) adding a product containing 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene taken out from an outlet of a continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 110g of the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 95%, and the purity is 98% by HPLC detection.
Example 4
A preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of trimethyl orthoformate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulating temperature of the continuous flow tubular reactor I to be 80 ℃ and stable, and setting the circulating temperature of the continuous flow tubular reactor II to be 30 ℃ and stable; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 50.0ml/min, and reacting for 5min at the temperature of 80 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) adding a product containing 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene taken out from an outlet of a continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 105g of the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 90 percent, and the purity is 98 percent by HPLC detection.
Example 5
A preparation method of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of trimethyl orthoformate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulating temperature of the continuous flow tubular reactor I to be 100 ℃ and stable, and setting the circulating temperature of the continuous flow tubular reactor II to be 30 ℃ and stable; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 150.0ml/min, and reacting for 5min at the temperature of 100 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) adding a product containing 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene taken out from an outlet of a continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 110g of the product 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 95%, and the purity is 98% by HPLC detection.
Example 6
A preparation method of 1,3, 5-triethoxy-2, 4, 6-trinitrobenzene specifically comprises the following steps:
(1) dissolving 100g of trinitrophloroglucinol into a beaker filled with 500g of triethyl orthoformate, and uniformly stirring to obtain a raw material solution, wherein the beaker is connected with a metering pump;
(2) setting the circulation temperature of the continuous flow tubular reactor I to be 110 ℃ and reaching stability, and setting the circulation temperature of the continuous flow tubular reactor II to be 30 ℃ and reaching stability; pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I through a metering pump at the flow rate of 150.0ml/min, and reacting for 5min at 110 ℃ to obtain an alkylation reaction liquid;
(3) feeding the alkylation reaction liquid in the step (2) into a continuous flow tubular reactor II for cooling, and cooling for 5min at the temperature of 30 ℃;
(4) and (3) adding the product containing the 1,3, 5-triethoxy-2, 4, 6-trinitrobenzene taken out from the outlet of the continuous flow tubular reactor II into 1500g of methanol solution, wherein the temperature of the methanol solution is 5 ℃, mechanically stirring for 1 hour, filtering, and drying the solid to obtain 125g of the product 1,3, 5-triethoxy-2, 4, 6-trinitrobenzene, wherein the yield is 95 percent, and the purity is 98 percent by HPLC (high performance liquid chromatography).
In the above embodiments provided by the present invention, the continuous flow technology is used to perform alkylation reaction, different reaction temperature regions are set, the continuous flow tubular reactor I is a high temperature region, the reaction is started at the high temperature region to obtain an alkylation reaction solution containing mononitro and dinitro intermediate state, and then the alkylation reaction solution is fed into the continuous flow tubular reactor II at the low temperature region, so that the temperature is reduced to suppress the side reaction of the intermediate state product, the coking and carbonization phenomena are avoided, and the alkylation process is not affected. The yield and the purity of the target product 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene are improved.
Meanwhile, in the step (4) in each of the above embodiments, after the obtained product is added into a methanol solution for crystallization and stirring, the filtrate obtained by filtration is fractionated and recovered to recover the alkylating reagent trimethyl orthoformate or dimethyl sulfate or triethyl orthoformate, thereby realizing zero emission and recycling.
It should be further clear to those skilled in the art that the preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene provided in the examples of the present invention is not limited to the preparation of 1,3, 5-trimethoxy-2, 4, 6-trinitrobenzene, 1,3, 5-triethoxy-2, 4, 6-trinitrobenzene, and other similar series such as 1,3, 5-tripropoxy-2, 4, 6-trinitrobenzene, 1,3, 5-triisopropoxy-2, 4, 6-trinitrobenzene, 1,3, 5-tributoxy-2, 4, 6-trinitrobenzene and related isomers can also be prepared by using the method provided in the present invention.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A preparation method of 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene is characterized by comprising the following steps:
(1) dissolving trinitrophloroglucinol into an alkylating reagent with the mass 5 times that of the trinitrophloroglucinol to obtain a raw material solution;
(2) pumping the raw material liquid obtained in the step (1) into a continuous flow tubular reactor I, and reacting for 5-30min at the temperature of 80-110 ℃ to obtain alkylation reaction liquid;
(3) feeding the alkylation reaction solution in the step (2) into a continuous flow tubular reactor II for cooling for 5-10min, wherein the circulating cooling temperature of the continuous flow tubular reactor II is 20-30 ℃;
(4) adding a product taken out from an outlet of the continuous flow tubular reactor II into a crystallization solution, cooling, crystallizing, stirring, filtering and drying to obtain a product 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene;
the alkylating agent is a methylating agent or an ethylating agent or a propylating agent.
2. The method for producing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the alkylating agent in step (1) is trimethyl orthoformate or dimethyl sulfate or triethyl orthoformate.
3. The method for preparing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the reaction temperature of the raw material liquid in the step (2) in the continuous flow tubular reactor I is 90-100 ℃ and the reaction time is 10-15 minutes.
4. The method for preparing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the crystallization solution in the step (4) is one or more of C1-C3 alcohols.
5. The method for preparing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the crystallization solution in the step (4) is one or more of methanol, ethanol and isopropanol.
6. The method for preparing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the weight ratio of the crystallization solution to the alkylating agent in the step (4) is 1: 1-10: 1.
7. the method for preparing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the temperature of the cooling crystallization process in the step (4) is 5-10 ℃.
8. The method for producing 1,3, 5-trialkoxy-2, 4, 6-trinitrobenzene according to claim 1, characterized in that the flow rate at which the raw material liquid is pumped into the continuous flow tube reactor I in step (1) is 10ml/min to 500 ml/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143629A (en) * | 2022-12-16 | 2023-05-23 | 中国科学院大连化学物理研究所 | A kind of continuous alkylation method of trinitrophloroglucinol |
| CN116813477A (en) * | 2023-06-14 | 2023-09-29 | 中国科学院大连化学物理研究所 | Method for continuously preparing trinitrobenzene |
-
2021
- 2021-07-27 CN CN202110849087.XA patent/CN113527105A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143629A (en) * | 2022-12-16 | 2023-05-23 | 中国科学院大连化学物理研究所 | A kind of continuous alkylation method of trinitrophloroglucinol |
| CN116813477A (en) * | 2023-06-14 | 2023-09-29 | 中国科学院大连化学物理研究所 | Method for continuously preparing trinitrobenzene |
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Application publication date: 20211022 |