CN114634416A - Preparation method of 2-chloro-2-nitropropane - Google Patents
Preparation method of 2-chloro-2-nitropropane Download PDFInfo
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- CN114634416A CN114634416A CN202210388855.0A CN202210388855A CN114634416A CN 114634416 A CN114634416 A CN 114634416A CN 202210388855 A CN202210388855 A CN 202210388855A CN 114634416 A CN114634416 A CN 114634416A
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Abstract
The invention discloses a preparation method of 2-chloro-2-nitropropane, which comprises the following steps: s1, sequentially adding hypochlorite and water into a three-neck flask provided with a thermometer and a solid feeder, and then placing the flask on a constant-temperature heating magnetic stirrer for stirring, wherein the reaction temperature is 0-50 ℃; s2, adding raw material acetone oxime into a three-neck flask in batches for reaction; s3, cooling the reaction liquid to room temperature after the reaction is finished, standing and layering the reaction liquid in a separating funnel, and separating out the lower layer solution of 2-chloro-2-nitropropane; the yield of the product 2-chloro-2-nitropropane obtained from S4 is 83.0-85.5%, and the purity is 99.5-99.6% by GC detection. The cost of the raw materials is greatly reduced; the method is a synthesis process, and avoids solvent recovery waste and environmental pollution caused by using a large amount of solvent; the invention can obtain the product only by standing and layering.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method of 2-chloro-2-nitropropane.
Background
2-chloro-2-nitropropane, also known as 2-nitro-2-chloropropane, is an organic synthetic reagent and can be used for preparing an explosive chemical marker DMNB. Is used as pesticide in agriculture and as solvent of hydrocarbon in chemical industry. In recent years, due to the influence of the increase of the demand of 2-chloro-2-nitropropane related manufactured products, the market demand of 2-chloro-2-nitropropane is expanded, and the industrialization of the 2-chloro-2-nitropropane has good market prospect and obvious economic benefit.
The synthesis of 2-chloro-2-nitropropane by chlorination of 2-nitropropane is a widely used process, the chlorinating agent being typically chlorine, NCS, carbon tetrachloride, oxalyl chloride, etc. The solvent is typically water, methanol, tetrahydrofuran, benzene, etc.
The method has the defects that the price of the raw material 2-nitropropane is high, most of the reaction needs to use solvents, which easily causes the waste of solvent recovery and environmental pollution, and chlorine and oxalyl chloride in the used chlorinated reagent have the defects of high toxicity and corrosivity; NCS is used as a chlorinated reagent to generate a large amount of solid waste in the post-treatment process; the relationship between the toxicity of carbon tetrachloride and the destruction of the ozone layer is rarely used at present.
There are also other methods:
bobinski, Thomas, reports a process for the synthesis of 2-chloro-2-nitropropane starting from acetoxime. The method needs two steps of reaction, chlorine and ozone are respectively used for chlorination and oxidation to generate 2-chloro-2-nitropropane, the chlorination reagent used in the method is a highly toxic gas with strong pungent smell, and the reaction yield is only 30 percent lower.
Disclosure of Invention
In view of the above-mentioned drawbacks or disadvantages of the prior art, it is desirable to provide a method for synthesizing 2-chloro-2-nitropropane from acetoxime by oxidative chlorination, so as to improve the conversion rate of acetoxime and the selectivity of 2-chloro-2-nitropropane.
According to the technical solution provided by the embodiment of the present application,
a method for synthesizing 2-chloro-2-nitropropane by oxidizing and chlorinating acetoxime, which comprises the following steps: the chlorinated oxidizing reagent used in the method is hypochlorite. Acetone oxime and hypochlorite react at a certain temperature to generate 2-chloro-2-nitropropane, and reaction liquid is stood for layering to obtain the product. The reaction equation is as follows:
the reaction materials of the invention are synthesized by one step, but the reaction mechanism is complex and comprises steps of oxidation, chlorination and the like, and the possible reaction mechanism is deduced as follows,
further, the method is implemented according to the following steps:
sequentially adding hypochlorite and water into a three-neck flask provided with a thermometer and a solid feeder, adding acetone oxime in batches at 0-50 ℃ under the condition of electric stirring, wherein the feeding and reaction time is controlled to be 0.5-5h, and the feeding amount in the early stage is preferably controlled to be less than 5 ℃ due to the reaction heat release; and standing and layering the obtained reaction solution in a separating funnel, wherein the separated lower layer is the product 2-chloro-2-nitropropane.
Further, the hypochlorite is one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, preferably sodium hypochlorite.
Further, hypochlorite is added in an amount of 3 to 10 times, preferably 3 to 5 times, as much as the raw material acetoxime.
Further, the reaction temperature is preferably 5 to 30 ℃.
Furthermore, the addition is preferably carried out by adding acetone oxime to the chloroxidizing agent in portions for 1 to 2 hours.
Further, the reaction time is preferably 1h to 2 h.
Hypochlorite refers to a compound containing hypochlorite ions (ClO)-) A salt wherein the chlorine has an oxidation state of + 1. Typically hypochlorite exists in solution, is unstable, and undergoes disproportionation to produce chlorate and chloride. Light is decomposed into chloride and oxygen. Common hypochlorites, including sodium hypochlorite (bleach) and calcium hypochlorite (bleach), are very powerful oxidants that react strongly exothermically with many organic compounds and may be burned.
Sodium hypochlorite, an inorganic compound of the chemical formula NaClO, is a hypochlorite salt and is the most common "chlorine" bleaching agent in household washing.
Sodium hypochlorite is mainly used in numerous fields such as bleaching, industrial wastewater treatment, papermaking, weaving, pharmacy, fine chemistry industry, sanitary disinfection, specifically is:
1. for bleaching pulp, textiles (such as cloth, towel, undershirt, etc.), chemical fibers and starch;
2. the soap making industry is used as a bleaching agent for grease;
3. the chemical industry is used for producing hydrazine hydrate, monochloramine and dichloroamine;
4. chlorinating agent for preparing cobalt and nickel;
5. the water treatment agent is used as a water purifying agent, a bactericide and a disinfectant;
6. the dye industry is used for manufacturing sulphur sapphire;
7. the organic industry is used for manufacturing a detergent for preparing acetylene by using chloropicrin and calcium carbide hydration;
8. agricultural and animal husbandry uses as disinfectants and deodorants for vegetables, fruits, feedlots, animal houses, and the like;
9. the food-grade sodium hypochlorite is used for sterilizing drinking water, fruits and vegetables and sterilizing food manufacturing equipment and appliances, but cannot be used in the food production process taking sesame as a raw material.
Acetoxime is an organic compound with the molecular formula of C3H7NO, white needle crystal. It is easily soluble in water, ethanol, ether and acetone, can be dissolved in acid and alkali, and is easily hydrolyzed in dilute acid. It evaporates quickly in air.
The solid feeder can continuously and automatically add the solid reagent.
To sum up, the beneficial effect of this application:
1) the raw material used by the method is acetone oxime, and compared with the raw material 2-nitropropane in the prior method, the cost of the raw material is greatly reduced.
2) The chlorinated oxidant is low-toxicity hypochlorite, and the reaction does not use solvent, so the method is a synthesis process, and avoids solvent recovery waste and environmental pollution caused by using a large amount of solvent.
3) The reaction solution post-treatment only needs to be kept stand for layering, and the product can be obtained.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is a GC detection spectrum of a product separated by a separating funnel according to the invention;
FIG. 2 is a schematic front view of the solids feeder of the present invention.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
In a 5L three-necked flask equipped with an electric stirrer, a thermometer and a solid feed port, 3736.17g of sodium hypochlorite solution was added at room temperature, and the available chlorine content was 13.0%. Under the conditions of stirring and temperature control of 15 ℃, 250g of acetone oxime is added into a three-mouth bottle in batches, and the adding time is 1.0 h. After the addition, the reaction was stirred at room temperature for 0.5 h. After the reaction, the reaction solution was placed in a separatory funnel and allowed to stand for layering, and the lower layer liquid was separated, i.e., 361.29g of the 2-chloro-2-nitropropane product, with a yield of 85.5%. And the purity is 99.6 percent through GC detection.
Example 2
1810.61g of sodium hypochlorite solid (content: 90%) and 1922.61g of water were sequentially charged into a 5L three-necked flask equipped with an electric stirrer, a thermometer and a solid charging port at room temperature. Under the conditions of stirring and temperature control of 15 ℃, 400g of acetone oxime is added into a three-mouth bottle in batches, and the adding time is 1.5 h. After the addition, the reaction was stirred at room temperature for 0.5 h. After the reaction, the reaction solution was placed in a separatory funnel and allowed to stand for layering, and the lower layer liquid was separated, i.e., 561.16g of the 2-chloro-2-nitropropane product, with a yield of 83.0%. The purity is 99.5 percent by GC detection.
The yield of the 2-chloro-2-nitropropane product is mass yield: the water content of the product separated by the separating funnel is measured by a Karl Fischer's water content measuring method to obtain the purity of the product, and then the yield of the 2-chloro-2-nitropropane product is calculated by the product volume, mass and molecular weight theory.
And m is the actual product quality separated by the separating funnel.
The method for detecting the purity of the 2-chloro-2-nitropropane comprises the following steps:
instrument 7890B
A sample inlet: 250 ℃, split ratio of 100: 1
A chromatographic column: DB-WAX 60m × 320 μm × 0.25 μm
Column temperature: initially 60 deg.C, holding for 5min, ramping to 90 deg.C at 10 deg.C/min, ramping to 220 deg.C at 30 deg.C/min, and holding for 8 min.
A detector: FID, 280 ℃, hydrogen gas 30ml/min, air 300 ml/min.
The detection profile is shown in FIG. 1.
The solid feeder can automatically add solid reagent continuously, and has the same function as a funnel, as shown in fig. 2.
The foregoing description is only exemplary of the preferred embodiments of the invention and is illustrative of the principles and techniques that may be employed. Meanwhile, the scope of the invention according to the present application is not limited to the technical solutions in which the above-described technical features are combined in a specific manner, and also covers other technical solutions in which the above-described technical features or their equivalent are combined arbitrarily without departing from the inventive concept described above. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (8)
1. A preparation method of 2-chloro-2-nitropropane is characterized by comprising the following steps: the reaction equation for acetoxime and hypochlorite is as follows:
2. the process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the method comprises the following steps:
the S1 three-neck flask is provided with a thermometer and a solid feeder, and hypochlorite, water and available chlorine are sequentially added into the three-neck flask: the mass ratio of water is 0.4:1, and then the mixture is placed on a constant-temperature heating magnetic stirrer to be stirred, and the reaction temperature is 0-50 ℃;
s2 addition of raw materials acetoxime, hypochlorite: the proportion of acetone oxime is 3-10:1, the raw material acetone oxime is added into a three-neck flask in batches for reaction, and the adding time is 1-2 h;
after the S3 addition is finished, continuously stirring for 0.5h at room temperature, wherein the total reaction time is 0.5h-5 h;
s4, cooling the reaction liquid to room temperature after the reaction is finished, standing and layering the reaction liquid in a separating funnel, and separating out the lower layer solution of 2-chloro-2-nitropropane;
s5 detects that the yield of the separated lower solution 2-chloro-2-nitropropane is 83.0-85.5%, and the purity is 99.5-99.6% by adopting GC detection.
3. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the hypochlorite is one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite.
4. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the hypochlorite is preferably sodium hypochlorite.
5. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: hypochlorite salt: the addition ratio of acetoxime is preferably 3-5: 1.
6. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the reaction temperature is preferably from 5 ℃ to 30 ℃.
7. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the reaction time is preferably 1h to 2 h.
8. The process for preparing 2-chloro-2-nitropropane as claimed in claim 1, wherein: the acetone oxime should preferably be fed in portions with a temperature rise of less than 5 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016135749A1 (en) * | 2015-02-23 | 2016-09-01 | Council Of Scientific & Industrial Research | Diosgenin acetate-isoxazole derivatives, process for preparation thereof and their antifungal activity |
| CN106631809A (en) * | 2016-10-10 | 2017-05-10 | 南京工业大学 | Green synthesis method for preparing nitroalkanes by oxime oxidation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016135749A1 (en) * | 2015-02-23 | 2016-09-01 | Council Of Scientific & Industrial Research | Diosgenin acetate-isoxazole derivatives, process for preparation thereof and their antifungal activity |
| CN106631809A (en) * | 2016-10-10 | 2017-05-10 | 南京工业大学 | Green synthesis method for preparing nitroalkanes by oxime oxidation |
Non-Patent Citations (3)
| Title |
|---|
| M.A. ZOLFIGOL ET AL.: "New Reagent for a One-Step Synthesis of Gem-Chloronitro Compounds from Oximes", 《J. IRAN. CHEM. SOC.》, vol. 8, no. 4, pages 1059 * |
| THOMAS BOBINSKI ET AL.: "2-Chloro-2-nitrosopropane", 《E-EROS ENCYCLOPEDIA OF REAGENTS FOR ORGANIC SYNTHESIS》, pages 3 * |
| 孙青 等: "肟类选冶药剂的合成与应用", 《矿产保护与利用》, no. 2, pages 10 - 16 * |
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