1, 1, 1, 3-tetrachloroacetone as well as preparation method and application thereof

Abstract

The invention belongs to the field of fine chemical synthesis, and particularly relates to high-purity 1, 1, 1, 3-tetrachloroacetone as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) in the presence of a catalyst, contacting 1, 1, 1-trichloroacetone with chlorine for chlorination to obtain a 1, 1, 1, 3-tetrachloroacetone crude product; (2) carrying out reduced pressure distillation on the 1, 1, 1, 3-tetrachloroacetone crude product, and collecting a distillate of which the main fraction is 1, 1, 1, 3-tetrachloroacetone; (3) carrying out solvent crystallization on the distilled liquid by using water as a solvent, and washing to obtain a 1, 1, 1, 3-tetrachloroacetone hydrate crystal; and (4) carrying out rotary evaporation on the hydrate crystal to remove moisture. The method disclosed by the invention can be used for preparing a large amount of standard substances of the impurity 1, 1, 1, 3-tetrachloroacetone of the 1, 1, 3-trichloroacetone, and the purity can reach 95% or above; the method is simple, and the obtained high-purity product can be used as a standard substance to accurately and effectively detect the content of impurity 1, 1, 1, 3-tetrachloroacetone in 1, 1, 3-trichloroacetone.

Description

Technical Field

[0001] This invention belongs to the field of fine chemical synthesis, and relates to 1,1,1,3-tetrachloroacetone, its preparation method and application. Background Technology

[0002] 1,1,3-Trichloroacetone is an important industrial raw material with extremely wide applications. It is used in the synthesis and research of anti-HIV drugs, imidazole heterocyclic compounds, and polycyclic or bridged ring compounds. In the pesticide field, it is a crucial raw material for the synthesis of highly effective and low-toxicity insecticides and herbicides. In the dye industry, it is used to synthesize some azo dyes, triphenylmethane, and fluorescent whitening agents. It is also an important raw material for many pharmaceutical intermediates, especially in the synthesis of folic acid.

[0003] Currently, the main method for producing trichloroacetone in China is the direct chlorination of acetone. This method produces trichloroacetone with low purity, containing various impurities such as monochloroacetone, 1,3-dichloroacetone, 1,1-dichloroacetone, 1,1,1-trichloroacetone, 1,1,1,3-tetrachloroacetone, 1,1,3,3-tetrachloroacetone, pentachloroacetone, and hexachloroacetone. Since trichloroacetone is an important raw material for folic acid synthesis, it is essential to determine its impurities and accurately measure the content of various impurities in 1,1,3-trichloroacetone before using it in the synthesis of pharmaceutical-grade folic acid. Therefore, preparing standards for 1,1,3-trichloroacetone impurities is crucial. Summary of the Invention

[0004] The purpose of this invention is to provide a method for synthesizing 1,1,1,3-tetrachloroacetone. This method can prepare a high-purity standard of 1,1,1,3-tetrachloroacetone, which can be used as a standard to accurately and effectively detect the content of this impurity in 1,1,3-tetrachloroacetone.

[0005] To achieve the above objectives, a first aspect of the present invention provides a method for preparing 1,1,1,3-tetrachloroacetone, the method comprising: (1) In the presence of a catalyst, 1,1,1-trichloroacetone was chlorinated by contacting chlorine gas to obtain crude 1,1,1,3-tetrachloroacetone; (2) The crude 1,1,1,3-tetrachloroacetone was subjected to vacuum distillation, and the distillate of the main fraction was collected as 1,1,1,3-tetrachloroacetone. (3) The distillate was subjected to solvent crystallization and washing with water to obtain 1,1,1,3-tetrachloroacetone hydrate crystals; (4) Remove the water from the hydrate crystals by rotary evaporation.

[0006] A second aspect of the present invention provides 1,1,1,3-tetrachloroacetone obtained by the method of the present invention.

[0007] A third aspect of the present invention provides the application of the 1,1,1,3-tetrachloroacetone described herein as an impurity standard for the gas phase detection of 1,1,3-trichloroacetone.

[0008] Compared with existing technologies, the method for synthesizing 1,1,1,3-tetrachloroacetone described in this invention has the following advantages through the above technical solution: The method for synthesizing 1,1,1,3-tetrachloropropanone of the present invention can be used to prepare standards of 1,1,3-tetrachloropropanone impurity 1,1,1,3-tetrachloropropanone in large quantities with a purity of over 95%. The method is simple, and the high-purity product obtained can be used as a standard to accurately and effectively detect the content of 1,1,1,3-tetrachloropropanone impurity in 1,1,3-tetrachloropropanone. Attached Figure Description

[0009] Figure 1 This is the gas chromatogram of the product of Example 1; Figure 2 This is the GC-MS image of the product from Example 1; Figure 3-1 , Figure 3-2 , Figure 3-3 , Figure 3-4 , Figure 3-5 and Figure 3-6 This is the 2D-NMR spectrum of the product from Example 1. Detailed Implementation

[0010] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0011] This invention provides a method for preparing 1,1,1,3-tetrachloroacetone, the method comprising: (1) In the presence of a catalyst, 1,1,1-trichloroacetone was chlorinated by contacting chlorine gas to obtain crude 1,1,1,3-tetrachloroacetone; (2) The crude 1,1,1,3-tetrachloroacetone was subjected to vacuum distillation, and the distillate of the main fraction was collected as 1,1,1,3-tetrachloroacetone. (3) The distillate was subjected to solvent crystallization and washing with water to obtain 1,1,1,3-tetrachloroacetone hydrate crystals; (4) Remove the water from the hydrate crystals by rotary evaporation.

[0012] The method for synthesizing 1,1,1,3-tetrachloropropanone described in this invention can be used to prepare large quantities of standards for 1,1,3-tetrachloropropanone impurities, with a purity of over 95%. The method is simple, and the high-purity product obtained can be used as a standard to accurately and effectively detect the content of 1,1,1,3-tetrachloropropanone impurities in 1,1,3-tetrachloropropanone.

[0013] In step (2) of the method of the present invention, according to a preferred embodiment of the present invention, the conditions for vacuum distillation include: collecting the fraction with a top temperature of 80-140°C at a vacuum degree between 0.07-0.10 MPa.

[0014] According to a preferred embodiment of the present invention, a fraction with a top temperature of 120-140°C is collected under a vacuum of 0.07-0.08 MPa.

[0015] According to a preferred embodiment of the present invention, a fraction with a top temperature of 100-120°C is collected under a vacuum of 0.08-0.09 MPa.

[0016] According to a preferred embodiment of the present invention, a fraction with a top temperature of 80-100°C is collected under a vacuum of 0.09-0.10 MPa.

[0017] According to a preferred embodiment of the present invention, the fraction with a top temperature of 92-98°C is collected when the vacuum degree is between 0.092 and 0.095 MPa.

[0018] According to a preferred embodiment of the present invention, a fraction with a top temperature of 105 to 115°C is collected under a vacuum of 0.085 to 0.090 MPa.

[0019] According to a preferred embodiment of the present invention, a fraction with a top temperature of 130 to 135°C is collected under a vacuum of 0.075 to 0.080 MPa.

[0020] In the method of the present invention, the solvent crystallization process in step (3) generally includes: crystallization preparation, crystal nucleation and crystal growth.

[0021] According to a preferred embodiment of the present invention, the conditions for crystallization preparation include: a temperature of 40-50°C and a weight ratio of solvent to distillate of 1:(0.5-2).

[0022] According to a preferred embodiment of the present invention, the conditions for crystallization nucleation include: a temperature of 15-20°C and a time of 40-50 min.

[0023] According to a preferred embodiment of the present invention, the crystal growth conditions include: a temperature of 8-13°C and a time of 80-100 min.

[0024] The method of the present invention does not have special requirements for washing. Generally, washing can be carried out with low-temperature water, with the temperature of the low-temperature water being 5-10℃.

[0025] In this invention, the conditions for rotary evaporation in step (4) can be selected from a wide range. According to a preferred embodiment of this invention, the rotary evaporation temperature is 70-95℃, the vacuum degree is 0.095-0.1MPa, and the rotary evaporation time is 30-60min.

[0026] In this invention, the catalyst has no special requirements. The following is an illustrative description, but it does not limit the scope of the invention. For example, the catalyst is one or more of Lewis acid, organic amine, and thiocyanate, preferably one or more of ferric chloride, aluminum chloride, triethylamine, and SO2Cl2.

[0027] In this invention, there are no special requirements for the amount of catalyst used. The following is an illustrative example, but it does not limit the scope of the invention. For example, the molar ratio of the catalyst to 1,1,1-trichloroacetone is 1:(10-20). In this invention, there are no special requirements for the molar ratio of chlorine to 1,1,1-trichloroacetone. The following is an illustrative example, but it does not limit the scope of the invention. For example, the molar ratio of chlorine to 1,1,1-trichloroacetone is 1:(0.5-2).

[0028] In this invention, there are no special requirements for the reaction time; generally, the contact time is 15-25 hours.

[0029] In this invention, there are no special requirements for the flow rate of chlorine gas. The flow rate can be adjusted appropriately according to the amount of raw materials such as 1,1,1-trichloroacetone added in the reaction. The gas flow rate should be stable and uniform and ensure that it is the target amount.

[0030] In this invention, there are no special requirements for the reaction temperature; for example, the reaction temperature is 40-100℃.

[0031] The method for synthesizing 1,1,1,3-tetrachloropropanone described in this invention can be used to prepare large quantities of 1,1,3-trichloropropanone impurity 1,1,1,3-tetrachloropropanone standards with a purity of over 90%. Thus, this invention provides 1,1,1,3-tetrachloropropanone obtained by the method described in this invention. Preferably, the purity of the 1,1,1,3-tetrachloropropanone liquid product is ≥95%.

[0032] The method of this invention is simple, and the high-purity product obtained can be used as a standard to accurately and effectively detect the content of 1,1,1,3-tetrachloropropanone, an impurity in 1,1,3-trichloropropanone. Therefore, this invention provides the application of the aforementioned 1,1,1,3-tetrachloropropanone as an impurity standard for the gas-phase detection of 1,1,3-trichloropropanone.

[0033] The reaction equation for the method of this invention is as follows:

[0034] Each step of the present invention is carried out under dynamic conditions as needed. There are no particular restrictions on the specific stirring operations used in the dynamic process. Those skilled in the art can use various operations conventionally used in the field.

[0035] The present invention will be described in detail below through embodiments.

[0036] In the following examples, the purity of 1,1,1,3-tetrachloroacetone was determined by gas chromatography; unless otherwise specified, all raw materials used were commercially available.

[0037] Example 1 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Triethylamine (20g, 0.198mol) was added to 1,1,1-trichloroacetone (500g, 3.10mol), stirred and heated to 75℃, 5.5mol of chlorine gas was introduced, and the reaction time was 21h to obtain crude 1,1,1,3-tetrachloroacetone.

[0038] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.092 to 0.095 MPa, and the temperature was increased. The distillate with a top temperature between 92 and 96°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (218 g).

[0039] (3) Add 130 g of water (7.26 mol) at 48°C to the distillate of 1,1,1,3-tetrachloroacetone, maintain stirring at 40-45°C, cool down to 18°C ​​after dissolving, stir for 42 min, observe the phenomenon of crystal precipitation, continue to cool down to 10°C, stir for 90 min, filter, wash the solid with 200 g of water at 8°C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0040] (4) The obtained solid was rotary evaporated under a vacuum of 0.098 MPa and heated to 80°C for 35 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone.

[0041] Gas phase detection results are shown below Figure 1 ,Depend on Figure 1It can be seen that the product has high purity, with the main peak appearing at 20.436 min, and the purity in the spectrum is 98.7%. See GC-MS Figure 2 ,Depend on Figure 2 Peaks can be observed at m / z 193.9, m / z 195.9, and m / z 197.9, which correspond to the molecular weight of 1,1,1,3-tetrachloroacetone (where...). 35 Cl and 37 The value of Cl is close to 158.9, which is most likely tetrachloroacetone losing a chlorine atom. The value of CCl3 corresponds to 77.0. + And m / z49.0 corresponds to CCl4 + In summary, based on the reaction process, the molecular structure is 1,1,1,3-tetrachloroacetone; 2D-NMR Figures 3-1 to 3-6 , Figure 3-1 It can be seen that the molecule contains only one type of hydrogen atom and is subject to a significant electron-withdrawing effect; Figure 3-2 It can be seen that the four carbon signals are carbonyl carbon at 183 ppm, CCl3 carbon at 93 ppm, the three peaks at 77 ppm are the special structure of CCl3-C=O, and CH2Cl carbon at 41 ppm. Figure 3-3 It can be seen that there is a negative peak, corresponding to the CH2 structure; Figure 3-4 The molecule contains only one set of hydrogen atoms on the CH2 group; Figure 3-5 The CH2Cl structure was confirmed; Figure 3-6 Upon further verification of the above results, it can be concluded that the compound is 1,1,1,3-tetrachloroacetone.

[0042] Example 2 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Anhydrous ferric chloride (58 g, 0.357 mol) was added to 1,1,1-trichloroacetone (1000 g, 6.192 mol), stirred and heated to 69 °C, 11.5 mol of chlorine gas was introduced, and the reaction time was 23 h to obtain crude 1,1,1,3-tetrachloroacetone.

[0043] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.085 to 0.090 MPa, and the temperature was increased. The distillate with a top temperature between 105 and 115°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (461 g).

[0044] (3) Add 250 g of water (13.89 mol) at 46 °C to the distillate of 1,1,1,3-tetrachloroacetone, maintain the temperature at 45-50 °C and stir. After dissolving, cool down to 15 °C and stir for 48 min. Observe the phenomenon of crystal precipitation. Continue to cool down to 9 °C and stir for 85 min. Filter and wash the solid with 500 g of water at 9 °C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0045] (4) The obtained solid was rotary evaporated under a vacuum of 0.097 MPa and heated to 80°C for 55 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone (purity 97.4%).

[0046] Example 3 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Anhydrous aluminum chloride (39.6 g, 0.297 mol) was added to 1,1,1-trichloroacetone (500 g, 3.10 mol), stirred and heated to 69 °C, 1.60 mol of chlorine gas was introduced, and the reaction time was 16 h to obtain crude 1,1,1,3-tetrachloroacetone.

[0047] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.075 to 0.080 MPa, and the temperature was increased in a gradient manner. The distillate with a top temperature between 130 and 135 °C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (183 g).

[0048] (3) Add 300g of water (16.7mol) at 48°C to the distillate of 1,1,1,3-tetrachloroacetone, maintain stirring at 45-50°C, cool down to 20°C after dissolving, stir for 40min, observe the phenomenon of crystal precipitation, continue to cool down to 8°C, stir for 80min, filter, wash the solid with 200g of water at 10°C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0049] (4) The obtained solid was rotary evaporated under a vacuum of 0.099 MPa and heated to 75°C for 40 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone (purity 97.3%).

[0050] Example 4 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Triethylamine (20g, 0.198mol) was added to 1,1,1-trichloroacetone (500g, 3.10mol), stirred and heated to 75℃, and 5.5mol of chlorine gas was introduced. The reaction time was 21h to obtain crude 1,1,1,3-tetrachloroacetone.

[0051] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.092 to 0.095 MPa, and the temperature was increased. The distillate with a top temperature between 125 and 130°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (209 g).

[0052] (3) Add 130 g of water (7.26 mol) at 48°C to the distillate of 1,1,1,3-tetrachloroacetone, maintain stirring at 40-45°C, cool down to 18°C ​​after dissolving, stir for 42 min, observe the phenomenon of crystal precipitation, continue to cool down to 10°C, stir for 90 min, filter, wash the solid with 200 g of water at 8°C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0053] (4) The obtained solid was rotary evaporated under a vacuum of 0.097 MPa and heated to 80°C for 52 min. After evaporation, the liquid in the bottle was removed, which was 1,1,1,3-tetrachloroacetone (purity 93.6%).

[0054] Example 5 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Triethylamine (20g, 0.198mol) was added to 1,1,1-trichloroacetone (500g, 3.10mol), stirred and heated to 75℃, and 5.5mol of chlorine gas was introduced. The reaction time was 21h to obtain crude 1,1,1,3-tetrachloroacetone.

[0055] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.092 to 0.095 MPa, and the temperature was increased. The distillate with a top temperature between 92 and 96°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (220 g).

[0056] (3) Add 130 g of water (7.26 mol) at 35°C to the distillate of 1,1,1,3-tetrachloroacetone, maintain stirring at 33-38°C, cool down to 19°C after dissolving, stir for 55 min, observe the phenomenon of crystal precipitation, continue to cool down to 15°C, stir for 60 min, filter, wash the solid with 200 g of water at 5°C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0057] (4) The obtained solid was rotary evaporated under a vacuum of 0.098 MPa and heated to 78°C for 45 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone (purity 92.6%).

[0058] Example 6 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Triethylamine (20g, 0.198mol) was added to 1,1,1-trichloroacetone (500g, 3.10mol), stirred and heated to 75℃, and 5.5mol of chlorine gas was introduced. The reaction time was 21h to obtain crude 1,1,1,3-tetrachloroacetone.

[0059] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.092 to 0.095 MPa, and the temperature was increased. The distillate with a top temperature between 92 and 96°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (210 g).

[0060] (3) Add 100 g of water (5.6 mol) at 45°C to the distillate of 1,1,1,3-tetrachloroacetone, maintain stirring at 40-45°C, cool down to 19°C after dissolving, stir for 42 min, observe the phenomenon of crystal precipitation, continue to cool down to 10°C, stir for 90 min, filter, wash the solid with 200 g of water at 8°C to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0061] (4) The obtained solid was rotary evaporated under a vacuum of 0.098 MPa and heated to 78°C for 45 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone (purity 93.8%).

[0062] Comparative Example 1 (1) 1,1,1-trichloroacetone (323g, 2.0mol) was added to a three-necked flask equipped with a reflux condenser. The flask was irradiated with a 275W sun lamp, and the oil bath temperature was set at 150℃. The 1,1,1-trichloroacetone in the flask was brought to a boil. After boiling, chlorine gas (4.0mol) was continuously introduced. As the reaction proceeded, the oil bath temperature was slowly increased, and the liquid in the flask was kept boiling throughout. The reaction took 42 hours. After purging with air for 2 hours, the reaction solution was removed to obtain crude 1,1,1,3-tetrachloroacetone.

[0063] (2) Distill 1,1,1,3-tetrachloropropanone crude product under reduced pressure, maintain vacuum degree of 0.090-0.094 MPa, raise temperature, and collect the distillate with top temperature between 100-106℃. The distillate obtained is 1,1,1,3-tetrachloropropanone (purity 81.3%).

[0064] Comparative Example 2 (1) Preparation of crude 1,1,1,3-tetrachloroacetone: Triethylamine (20g, 0.198mol) was added to 1,1,1-trichloroacetone (500g, 3.10mol), stirred and heated to 75℃, and 5.5mol of chlorine gas was introduced. The reaction time was 21h to obtain crude 1,1,1,3-tetrachloroacetone.

[0065] (2) The crude 1,1,1,3-tetrachloroacetone obtained in step (1) was subjected to vacuum distillation, maintaining a vacuum of 0.092 to 0.095 MPa, and the temperature was increased. The distillate with a top temperature between 92 and 96°C was collected. The distillate obtained was mainly composed of 1,1,1,3-tetrachloroacetone (203g).

[0066] (3) Add 280g of 50% ethanol aqueous solution at 45℃ to the distillate of 1,1,1,3-tetrachloroacetone, and stir at 40-45℃. After dissolving, cool down to 19℃ and stir for 0.5h to precipitate crystals. Continue to cool down to 10℃ and stir for 90min. Filter and wash the solid with 180g of 50% ethanol aqueous solution at 8℃ to obtain 1,1,1,3-tetrachloroacetone hydrate crystals.

[0067] (4) The obtained solid was rotary evaporated under a vacuum of 0.096 MPa and heated to 80°C for 50 min. After evaporation, the liquid in the bottle was removed, which is 1,1,1,3-tetrachloroacetone (purity 85.6%).

[0068] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing 1,1,1,3-tetrachloroacetone, characterized in that, The method includes: (1) In the presence of a catalyst, 1,1,1-trichloroacetone was contacted with chlorine gas for chlorination to obtain crude 1,1,1,3-tetrachloroacetone; (2) The crude 1,1,1,3-tetrachloroacetone was subjected to vacuum distillation, and the distillate of the main fraction was collected as 1,1,1,3-tetrachloroacetone. (3) The distillate was subjected to solvent crystallization and washing with water as a solvent to obtain 1,1,1,3-tetrachloroacetone hydrate crystals; (4) Remove the water from the hydrate crystals by rotary evaporation.

2. The method according to claim 1, wherein, In step (2), the conditions for vacuum distillation include: When the vacuum degree is between 0.07 and 0.10 MPa, the fraction with a top temperature of 80-140℃ is collected.

3. The method according to claim 2, wherein, In step (2), the conditions for vacuum distillation include: Collect the fraction with a top temperature of 120-140℃ under a vacuum of 0.07-0.08 MPa; and / or Collect the fraction with a top temperature of 100-120℃ under a vacuum of 0.08-0.09 MPa; and / or Collect the fraction with a top temperature of 80-100℃ under a vacuum of 0.09-0.10 MPa; and / or Collect the fraction with a top temperature of 92-98℃ under a vacuum of 0.092–0.095 MPa; and / or Collect the fraction with a top temperature of 105–115 °C at a vacuum of 0.085–0.090 MPa; and / or When the vacuum degree is between 0.075 and 0.080 MPa, the fraction with a top temperature of 130 to 135 °C is collected.

4. The method according to any one of claims 1-3, wherein, In step (3), The solvent crystallization process includes: crystallization preparation, crystal nucleation, and crystal growth; The conditions for crystallization preparation include: a temperature of 40-50℃ and a solvent to distillate weight ratio of 1:(0.5-2). The conditions for crystallization nucleation include: a temperature of 15-20℃ and a time of 40-50 min; The conditions for crystal growth include a temperature of 8-13℃ and a time of 80-100 min.

5. The method according to any one of claims 1-4, wherein, In step (3), Washing is performed using low-temperature water, with the water temperature being 5-10℃.

6. The method according to any one of claims 1-5, wherein, In step (4), The rotary evaporation temperature is 70-95℃, the vacuum degree is 0.095-0.1MPa, and the rotary evaporation time is 30-60min.

7. The method according to any one of claims 1-6, wherein, In step (1), The catalyst is one or more of Lewis acid, organic amine, and thioyl chloride, preferably one or more of ferric chloride, aluminum chloride, triethylamine, and SO2Cl2.

8. The method according to any one of claims 1-7, wherein, In step (1), The molar ratio of the catalyst to 1,1,1-trichloroacetone is 1:(10-20). The molar ratio of chlorine to 1,1,1-trichloroacetone is 1:(0.5-2); and / or The contact time is 15-25 hours; and / or The contact temperature is 40-100℃.

9. The 1,1,1,3-tetrachloroacetone obtained by the method according to any one of claims 1-8, Preferably, the purity of the 1,1,1,3-tetrachloroacetone liquid product is ≥95%.

10. The application of 1,1,1,3-tetrachloroacetone as described in claim 9 as an impurity standard for the gas phase detection of 1,1,3-trichloroacetone.

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