CN114292178A - Synthetic method of 2-chloro-1- (1-chlorocyclopropyl) ethanone - Google Patents
Synthetic method of 2-chloro-1- (1-chlorocyclopropyl) ethanone Download PDFInfo
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- CN114292178A CN114292178A CN202111595961.8A CN202111595961A CN114292178A CN 114292178 A CN114292178 A CN 114292178A CN 202111595961 A CN202111595961 A CN 202111595961A CN 114292178 A CN114292178 A CN 114292178A
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Abstract
The invention discloses a method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone, which comprises the following steps: s1, dissolving cyclopropyl methyl ketone IV serving as a raw material by adopting a solvent, adding a compound containing metallic aluminum serving as a catalyst, and introducing chlorine gas for chlorination reaction to obtain a chlorinated product: 2-chloro-1- (1-chlorocyclopropyl) ethanone I, 1- (1-chlorocyclopropyl) ethanone II and 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone III; s2, carrying out reduced pressure distillation on the chlorinated product to remove the solvent, and rectifying to obtain the 2-chloro-1- (1-chlorocyclopropyl) ethanone.
Description
Technical Field
The invention relates to a synthetic method of 2-chloro-1- (1-chlorocyclopropyl) ethanone, belonging to the technical field of chemical synthesis.
Background
Prothioconazole is a novel broad-spectrum triazolethione bactericide developed and created by Bayer company, and 2-chloro-1- (1-chlorocyclopropyl) ethanone is an important intermediate for synthesizing prothioconazole, but in the prior art, the synthesis technology is less, the synthesis yield is lower, the purity is not high, and the product contains various impurities, so that the industrialization degree is lower.
For example, in most processes in the prior art, 1- (1-chlorocyclopropyl) ethanone is used as a raw material, sulfuryl chloride is used as a chlorinating reagent for synthesis at low temperature, the conversion rate of chlorinated products is low, dichloro and trichloro impurities are high, and the product yield is low and is only about 75%. And sulfuryl chloride is a strong acid corrosive reagent, and when the sulfuryl chloride is used as a chlorination reagent, a large amount of toxic gases, namely sulfur dioxide and hydrogen chloride, can be generated in the reaction, and the generated mixed tail gas has great harm to the environment and human bodies. With the improvement of the requirement on environmental protection, the treatment method of the chlorination reaction tail gas is required to be higher and higher, and the production cost is increased.
Chlorine gas is widely paid attention to as a chlorination reagent recently, because chlorine gas only generates hydrogen chloride gas as the chlorination reagent, multi-stage absorption can be carried out by water to obtain hydrogen chloride water solutions with different concentrations, and the hydrochloric acid water solution has no other impurities, can also be applied to other industrial production, and meets the requirement of environmental protection. However, chlorine gas as a chlorinating reagent still has the problems of poor selectivity, low yield, difficult control of dichloro and trichloro impurities at methyl positions, and the like, although no sulfur dioxide gas is generated as the chlorinating reagent.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing 2-chloro-1- (1-chloro-cyclopropyl) ethanone, which takes cyclopropyl methyl ketone as a raw material, chlorine as a chlorination reagent and selects a catalyst with good catalytic effect and high selectivity to carry out chlorination reaction, so that the reaction conversion rate is improved, and further, the reaction yield is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone comprises the following steps:
s1, dissolving cyclopropyl methyl ketone IV serving as a raw material by adopting a solvent, adding a compound containing metallic aluminum serving as a catalyst, and introducing chlorine gas for chlorination reaction to obtain a chlorinated product: 2-chloro-1- (1-chlorocyclopropyl) ethanone I, 1- (1-chlorocyclopropyl) ethanone II and 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone III;
s2, carrying out reduced pressure distillation on the chlorinated product to remove the solvent, and rectifying to obtain 2-chloro-1- (1-chlorocyclopropyl) ethanone;
the reaction process is as follows:
the technical scheme of the invention is further improved as follows: the compound containing metallic aluminum in step S1 is MeAlCl2、Me2AlCl or MeAlCl2With Me2Mixtures of AlCl.
The technical scheme of the invention is further improved as follows: the dosage of the compound containing metallic aluminum is 0.5-10% of the mol number of the cyclopropylmethyl ketone.
The technical scheme of the invention is further improved as follows: in the step S1, the solvent is one or a mixture of two of dichloromethane, dichloroethane, methanol and toluene.
The technical scheme of the invention is further improved as follows: the weight ratio of the cyclopropylmethyl ketone to the solvent is 0.5-4.0: 1.
The technical scheme of the invention is further improved as follows: the chlorine gas introduction amount is 2.0-2.5 eq of the cyclopropyl methyl ketone, and the introduction rate is 20-80 g/h.
The technical scheme of the invention is further improved as follows: the reaction temperature of the step S1 is-5-15 ℃.
The technical scheme of the invention is further improved as follows: the rectification condition in the step S2 is-0.1 to-0.95 MPa, and the gas phase extraction temperature of the 2-chloro-1- (1-chlorocyclopropyl) ethanone is 100 to 102 ℃.
The technical scheme of the invention is further improved as follows: the pressure of the reduced pressure distillation in the step S2 is-0.95 to-0.1 MPa, and the temperature is 30 to 35 ℃.
Due to the adoption of the technical scheme, the invention has the technical progress that:
in the synthesis method of the 2-chloro-1- (1-chlorocyclopropyl) ethanone, raw materials are cheap and easy to obtain, the reaction condition is mild, sulfur dioxide is not generated in the reaction, the corrosivity to equipment is small, and the method is more green and environment-friendly compared with the existing process; by adding a compound containing metallic aluminum as a catalyst and controlling reaction conditions, the selectivity of chlorination reaction is effectively improved, and the conversion rate and the yield are improved; meanwhile, the distillate before rectification can be recycled to the reaction, the raw materials are effectively utilized, the chlorination reaction yield is improved by about ten percent, the reaction cost and the energy consumption are obviously reduced, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a diagram of the reaction process of the present invention.
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 with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reaction process of the present invention is shown in FIG. 1. In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
100g of dichloroethane, (200g, 2.378mol) of cyclopropylmethyl ketone are added into a 500mL four-neck flask, the temperature is reduced to-5 ℃, and (1.34g, 11.8mmol) of MeAlCl is added under stirring2Introducing chlorine gas at a rate of about 25g/h, performing three-stage absorption on the tail gas by using water, introducing the gas for 14.0h, detecting the relative contents of 2-chloro-1- (1-chlorocyclopropyl) ethanone 4.2%, 2-chloro-1- (1-chlorocyclopropyl) ethanone 93.8%, 2-dichloro-1- (1-chlorocyclopropyl) ethanone 1.8% by using gas chromatography, and slowly raising the temperature under reduced pressureThe solvent is removed by warming to 30 ℃. Under the vacuum of-0.1 MPa, a 50cm rectifying column and glass ring packing are used for carrying out rectification reaction, the temperature is slowly raised to 130 ℃, the fraction at the temperature of 100-102 ℃ is collected to obtain 2-chloro-1- (1-chlorocyclopropyl) ethanone, and the fraction at the temperature of 82.5-82.6 ℃ is recycled for reaction to obtain 341.7g of the product 2-chloro-1- (1-chlorocyclopropyl) ethanone, wherein the content is 97%, and the yield is 91.0%.
The product is confirmed to be 2-chloro-1- (1-chlorocyclopropyl) ethanone by nuclear magnetic resonance:
1HNMR(400MHz，CDCl3)δppm：4.54(s，1H)，1.62(m，2H)，1.36 (m，2H)
LC-MS[M+H]+：154.0019。
example 2
Charging (200g, 2.378mol) cyclopropylmethyl ketone into a 500ml four-necked flask, cooling to 10 ℃ and charging 150g of dichloroethane, charging (4.4g, 47.6mmol) Me with stirring2And introducing chlorine into AlCl at the introduction rate of about 60g/h, performing three-stage absorption on tail gas by using water, reacting for 6.5h, detecting the relative contents of 2-chloro-1- (1-chlorocyclopropyl) ethanone by using a gas chromatography, obtaining the product, namely 5.4%, 93.5% and 0.9% of 2-chloro-1- (1-chlorocyclopropyl) ethanone, and slowly heating to 30 ℃ under reduced pressure to remove the solvent. Rectifying by using a 50cm rectifying column and glass ring packing under the vacuum of-0.1 MPa, slowly heating to 130 ℃, collecting the fraction at the temperature of 99.6-102 ℃ to obtain 2-chloro-1- (1-chloro cyclopropyl) ethanone, and carrying out a loop reaction on the fraction at the temperature of 82.5-82.7 ℃ to obtain 339.6g of a product, wherein the content is 96%, and the yield is 89.6%.
Example 3
Adding (200g, 2.378mol) cyclopropylmethyl ketone into a 1000ml four-neck flask, cooling to 15 ℃, adding 200g of dichloromethane, adding (8.95g, 95mmol) MeAlCl under stirring2And (3.67g, 39.6mmol) Me2Introducing AlCl into chlorine gas at the introduction rate of about 75g/h, performing three-stage absorption on tail gas by using water, reacting for 3.5h, detecting 2.4% of 2-chloro-1- (1-chlorocyclopropyl) ethanone, 95.2% of 2-chloro-1- (1-chlorocyclopropyl) ethanone and 2.1% of 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone by using a gas chromatography, slowly heating to 30 ℃ under reduced pressure after the reaction is finished, removing dichloromethane, and performing vacuum distillation at-0.1 MPa by using a 50cm rectifying column and a glass ring under the vacuum condition of-0.1 MPaRectifying the filler, slowly heating to 130 ℃, collecting the fraction at 100-102 ℃ to obtain 2-chloro-1- (1-chlorocyclopropyl) ethanone, and carrying out a recycling reaction on the fraction at 82.4-82.8 ℃ to obtain 343.4g of a product with the content of 96% and the yield of 90.6%.
Example 4
Charging (500g, 5.95mol) cyclopropylmethyl ketone into a 2000ml four-necked flask, cooling to 10 ℃, charging 250g of dichloromethane, charging (44g, 0.48mol) Me under stirring2Introducing AlCl into chlorine gas at a rate of about 60g/h, connecting tail gas with an absorption device, performing three-stage absorption with water, reacting for 5.0h, detecting 3.1% of 2-chloro-1- (1-chlorocyclopropyl) ethanone, 94.3% of 2-chloro-1- (1-chlorocyclopropyl) ethanone and 2.3% of 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone by gas chromatography, slowly heating to 30 ℃ to remove dichloromethane after the reaction is finished and under reduced pressure, rectifying by using a 50cm rectifying column and a glass ring filler under vacuum of-0.1 MPa, slowly heating to 130 ℃ to collect fraction at 100-102 ℃ to obtain 2-chloro-1- (1-chlorocyclopropyl) ethanone, and mechanically reacting the fraction at 82.3-83.0 ℃ to obtain 864.1g of the product 2-chloro-1- (1-chlorocyclopropyl) ethanone, the content is 95.4 percent, and the product yield is 90.5 percent.
Comparative example
Adding 100g of cyclopropylmethyl ketone into a 500mL four-mouth bottle, cooling to 15 ℃, adding 50g of dichloromethane, introducing chlorine at the introduction rate of about 60g/h, connecting tail gas with an absorption device, performing three-stage absorption by using water, reacting for 10.0h, detecting products 2-chloro-1- (1-chlorocyclopropyl) ethanone 11.8%, 2-chloro-1- (1-chlorocyclopropyl) ethanone 75.6% and 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone 12.1% by using gas chromatography, cooling to 30 ℃ after the reaction is finished, removing the solvent by reduced pressure distillation to obtain a product 2-chloro-1- (1-chlorocyclopropyl) ethanone 246.2g with the content of 50.1% and the impurity 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone (III) which is obviously increased, the product yield was 67.8%.
In the above examples and comparative examples, the purity of the product was checked by gas chromatography under the following specific test conditions:
the DM-624 chromatographic column has a sample inlet temperature of 250 ℃, a detector temperature of 300 ℃, no flow division, an air flow rate of 400mL/min, a hydrogen flow rate of 30mL/min, a tail blowing flow rate of 25mL/min, a column temperature adopting a programmed temperature: keeping the temperature at 70 ℃ for 1min, increasing the temperature to 150 ℃ at 5 ℃/min, increasing the temperature to 239 ℃ at 20 ℃/min, and keeping the temperature for five minutes.
The product quantification takes a 98 percent reagent pure product purchased from 2-chloro-1- (1-chlorocyclopropyl) ethanone as a quantitative standard product and takes n-decane as an internal standard substance to quantify by adopting an internal standard method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A synthetic method of 2-chloro-1- (1-chlorocyclopropyl) ethanone is characterized by comprising the following steps: the method comprises the following steps:
s1, dissolving cyclopropyl methyl ketone IV serving as a raw material by adopting a solvent, adding a compound containing metallic aluminum serving as a catalyst, and introducing chlorine gas for chlorination reaction to obtain a chlorinated product: 2-chloro-1- (1-chlorocyclopropyl) ethanone I, 1- (1-chlorocyclopropyl) ethanone II and 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone III;
s2, carrying out reduced pressure distillation on the chlorinated product to remove the solvent, and rectifying to obtain 2-chloro-1- (1-chlorocyclopropyl) ethanone;
the reaction process is as follows:
2. the method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: the compound containing metallic aluminum in step S1 is MeAlCl2、Me2AlCl or MeAlCl2With Me2Mixtures of AlCl.
3. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 2, characterized in that: the dosage of the compound containing metallic aluminum is 0.5-10% of the mol number of the cyclopropylmethyl ketone.
4. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: in the step S1, the solvent is one or a mixture of two of dichloromethane, dichloroethane, methanol and toluene.
5. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 4, wherein: the weight ratio of the cyclopropylmethyl ketone to the solvent is 0.5-4.0: 1.
6. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: the chlorine gas introduction amount is 2.0-2.5 eq of the cyclopropyl methyl ketone, and the introduction rate is 20-80 g/h.
7. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: the reaction temperature of the step S1 is-5-15 ℃.
8. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: the rectification condition in the step S2 is-0.1 to-0.95 MPa, and the gas phase extraction temperature of the 2-chloro-1- (1-chlorocyclopropyl) ethanone is 100 to 102 ℃.
9. The method for synthesizing 2-chloro-1- (1-chlorocyclopropyl) ethanone according to claim 1, characterized in that: the pressure of the reduced pressure distillation in the step S2 is-0.95 to-0.1 MPa, and the temperature is 30 to 35 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602365A (en) * | 2017-09-27 | 2018-01-19 | 长治市晋宁化工有限公司 | A kind of preparation method of 2 chlorine 1 (1 chlorine cyclopropyl) ethyl ketones |
| CN108586220A (en) * | 2018-06-27 | 2018-09-28 | 安徽国星生物化学有限公司 | A kind of synthetic method of the chloro- 1- of 2- (1- chlorine cyclopropyl) ethyl ketone |
| CN109748783A (en) * | 2019-01-31 | 2019-05-14 | 河北诚信集团有限公司 | A kind of preparation method of the chloro- 1- of 2- (1- chlorine cyclopropyl) ethyl ketone |
| CN112574141A (en) * | 2020-12-25 | 2021-03-30 | 河北威远生物化工有限公司 | Synthesis method of beta-chloro alpha, gamma-dicarbonyl compound |
| CN113511964A (en) * | 2021-03-18 | 2021-10-19 | 京博农化科技有限公司 | Synthetic method of high-content 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone for quantitative and qualitative analysis |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602365A (en) * | 2017-09-27 | 2018-01-19 | 长治市晋宁化工有限公司 | A kind of preparation method of 2 chlorine 1 (1 chlorine cyclopropyl) ethyl ketones |
| CN108586220A (en) * | 2018-06-27 | 2018-09-28 | 安徽国星生物化学有限公司 | A kind of synthetic method of the chloro- 1- of 2- (1- chlorine cyclopropyl) ethyl ketone |
| CN109748783A (en) * | 2019-01-31 | 2019-05-14 | 河北诚信集团有限公司 | A kind of preparation method of the chloro- 1- of 2- (1- chlorine cyclopropyl) ethyl ketone |
| CN112574141A (en) * | 2020-12-25 | 2021-03-30 | 河北威远生物化工有限公司 | Synthesis method of beta-chloro alpha, gamma-dicarbonyl compound |
| CN113511964A (en) * | 2021-03-18 | 2021-10-19 | 京博农化科技有限公司 | Synthetic method of high-content 2, 2-dichloro-1- (1-chlorocyclopropyl) ethanone for quantitative and qualitative analysis |
Non-Patent Citations (2)
| Title |
|---|
| CARLSON ROLF: "Halogenation of Enamines.II.Regiospecific Synthesis of Halomethyl Ketones" * |
| SAKAI, TAKASHI等: "Favorskii-type rearrangement of α,α\'-dihalo ketones with sodiomalonates leading to conjugated enone derivatives" * |
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