CN108084001A - A kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes - Google Patents
A kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes Download PDFInfo
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- CN108084001A CN108084001A CN201611049186.5A CN201611049186A CN108084001A CN 108084001 A CN108084001 A CN 108084001A CN 201611049186 A CN201611049186 A CN 201611049186A CN 108084001 A CN108084001 A CN 108084001A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention discloses a kind of synthetic method of improved 1 acetyl group, 1 chlorcyclopropane, this method, for raw material, heats reaction with 3,5 dichloro, 2 pentanone in inorganic base and organic solvent, using the reaction condition after optimization, the product using rectifying mode synthesizing and purifying.Technical solution using the present invention not only reduces production price, while reduces the generation of spent solvent, avoids pollution environment, in addition rectification process is easy to operate, easy to operate, in the industrial production can be widely used, is conducive to the industrialization of product.
Description
Technical field：
The present invention relates to a kind of chemical pesticide production fields, and in particular to a kind of synthetic method of pesticide intermediate.
Technical background：
Prothioconazoles are a kind of New-type wide-spectrum triazolinthione series bactericidal agents, are mainly used for preventing wheat, barley, rape, flower
Numerous diseases on the crops such as raw, rice and beans, and almost there is good control effect to all wheat class diseases.The sterilization
Agent has many advantages, such as wide spectrum, low toxicity, interior to inhale, holding effect is long, and spraying method is various, no environmental risk focus, is generally acknowledged
One of most promising triazole bactericidal agent.
As intermediate important in prothioconazoles building-up process, the synthesis of 1- acetyl-1-chlorcyclopropanes increasingly by
To the concern of research staff, the common method for synthesizing 1- acetyl-1-chlorcyclopropanes at present is to slough 3,5- Dichloro-2-pentanones
One molecule hydrogen chloride, so as to obtain product.It discloses a kind of utilization fluorine chlorine in patent CN104672074 to exchange, then defluorinate takes off
Chlorine obtains the method for 1- acetyl-1-chlorcyclopropanes, but there are impurity 1- acetyl group -1- fluorine cyclopropane in this method, it is difficult to
It is separated with product；The simultaneous reactions time is very short, it is necessary to strictly control reaction condition, otherwise can generate a large amount of impurity, reacts item
Part is relatively harsh；In addition there are a large amount of fluorine ions, severe corrosion equipments in reacting.
Disclosed in patent CN101759539 it is a kind of using phase transfer catalyst, it is anti-by 3,5- Dichloro-2-pentanones and alkali
The method that 1- acetyl-1-chlorcyclopropanes should be synthesized, wherein phase transfer catalyst are three alkane of tetraalkylammonium halides and halogenated aryl
Base ammonium.But this method is used, on the one hand it is the phase transfer catalyst of higher price to be used, on the other hand since product is in alkali
Under the conditions of and it is unstable, reaction system still keeps alkalescence, it is necessary to by product Fast Classification after the completion of reaction, otherwise can generate big
Tar is measured, difficulty is brought for the processing of subsequent technique.
The content of the invention：
In order to improve the prior art, a kind of synthesis of 1- acetyl-1-chlorcyclopropanes easy to operate, yield is higher is invented
Method, the present invention propose a kind of new synthesis technology, and particular content is as follows：
A kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes, chemical equation are：
Synthetic method comprises the following steps：
A mixes inorganic base and organic solvent, under stirring condition, is heated to certain temperature；
B maintains step a temperature, and to add raw material 3 into the reaction solution of step a in batches or in a manner of dropwise addition, 5- bis- is chloro-
2 pentanone；
After c is added dropwise to complete, continue to keep thermotonus 0.5-10h；
20-30 DEG C is cooled to after the completion of d reactions, filters, takes filtrate；
Filtrate rectifying, first recycling design are continued rectifying and obtain product by e.
Inorganic base refers to the one or more in carbonate, bicarbonate, preferably sodium carbonate, carbon wherein described in step a
One or more in sour potassium, sodium acid carbonate, saleratus；
The organic solvent refers to acetonitrile, benzene,toluene,xylene, dichloromethane, chloroform, carbon tetrachloride, two chloroethenes
Alkane, ethyl acetate, methyl acetate, ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, petroleum ether, pentane, just oneself
One kind in one or more in alkane, hexamethylene, heptane, preferably acetonitrile, toluene, ethyl acetate；
Certain temperature is heated to described in the step a, refers to be heated to 30-110 DEG C；
The molal weight ratio of inorganic base and raw material 3,5- Dichloro-2-pentanones is 1:1~3:1；It is preferred that 1.5:1；Step e
In, pressure 0.01-0.15MPa, temperature is 80-120 DEG C, preferably 100 DEG C.
By measuring, the product of technical solution of the present invention synthesis, reaction yield is not less than 82.0%, and separation yield is not less than
76.0%；
Beneficial effects of the present invention are：
Using technical solution of the present invention, production can be reduced to avoid the phase transfer catalyst of higher price is used
Price, the optional scope of solvent is big used by simultaneous reactions, and alkane solvents can be used for esters solvent, ether solvent；
Product, recycling design are obtained using rectificating method, the solvent enable repeatedly uses, and reduces the generation of spent solvent,
Pollution environment is avoided, rectificating method is easy to operate, easy to operate, in the industrial production can be widely used, convenient for improving product
Purity.
Description of the drawings：
Fig. 1 is the GC analysis charts of 1 products obtained therefrom of embodiment
Fig. 2 is the MS analysis charts of 1 products obtained therefrom of embodiment
Specific embodiment：
Technical scheme is further discussed in detail with reference to embodiments, it is necessary to explanation is, implemented
Example is only used for that present invention is explained further, and those skilled in the art of the present technique is facilitated to understand, is not intended to limit the protection of the present invention
Scope, related personnel change to of the invention obvious, still the present invention claims protection domain within.
Embodiment 1：
In 250ml four-hole bottles, sodium carbonate (0.15mol) is added in, acetonitrile 100g starts to stir, and system adds 80-85 DEG C,
3,5- Dichloro-2-pentanones (0.1mol) are added dropwise in (80-85 DEG C) of this temperature, and 10min drops finish, insulation reaction 5-6h, and inspection is controlled in gas phase
Survey 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, filters, filtrate rectifying recycling acetonitrile, and kettle is residual
Continue rectifying, obtain product (weight 9.8g).Reaction yield is 85.0%, separation yield 83.0%.
Embodiment 2：
In 250ml four-hole bottles, sodium acid carbonate (0.3mol) is added in, acetonitrile 100g starts to stir, and system heats 80-85 DEG C,
3,5- Dichloro-2-pentanones (0.1mol) being added dropwise for (80-85 DEG C) in this temperature, 10min drops finish, insulation reaction 10h, are controlled in gas phase,
Detect 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, filters, and solvent is collected in filtrate rectifying, after
Continuous rectifying obtains product, weight 9.30g, reaction yield 83.1%, separation yield 80.4%.
Embodiment 3：
In 250ml four-hole bottles, sodium carbonate (0.15mol) is added in, N-Methyl pyrrolidone 100g starts to stir, and system adds
Hot 100-110 DEG C, 3,5- Dichloro-2-pentanones (0.1mol) are added dropwise for (100-110 DEG C) in this temperature, 10min drops finish, insulation reaction
2h is controlled in gas phase, detects 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, filters, filtrate rectifying
Collect solvent and product.Weight is 9.4g, reaction yield 82.8%, separation yield 79.3%.
Embodiment 4：
In 250ml four-hole bottles, sodium acid carbonate (0.3mol) is added in, toluene 100g starts to stir, and system heats 110 DEG C and returns
In this temperature 3,5- Dichloro-2-pentanones (0.1mol) are added dropwise for (110 DEG C) in stream, and 10min drops finish, insulation reaction 12h, are controlled in gas phase,
Detect 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, filters, and solvent and production are collected in filtrate rectifying
Product.Weight is 9.1g, reaction yield 82.3%, separation yield 76.7%.
Embodiment 5：
In 250ml four-hole bottles, sodium carbonate (0.2mol) is added in, butyl acetate 100g starts to stir, and system heats 100 DEG C
In this temperature 3,5- Dichloro-2-pentanones (0.1mol) are added dropwise for (100 DEG C) in reflux, and 10min drops finish, insulation reaction 10h, in gas phase
Control detects 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, filters, and solvent is collected in filtrate rectifying
With product.Weight is 9.2g, reaction yield 83.2%, separation yield 78.6%.
Contrast test：
In 250ml four-hole bottles, sodium hydroxide (0.12mol, 25% aqueous solution) is added in, four butyl bromation amine 1g, system adds
Hot 95-100 DEG C, 3,5- Dichloro-2-pentanones (0.1mol) are added dropwise for (95-100 DEG C) in this temperature, 10min drops finish, insulation reaction
20min is controlled in gas phase, detects 3,5- Dichloro-2-pentanones<1%, it is considered as reaction and finishes, system is cooled to 25 DEG C, extracts, filtrate
Rectifying obtains product.Obtain product 8.7g, reaction yield 78%, separation yield 73%.
Technical solution of the present invention, which is can be seen that, by above example and comparative examples utilizes improved synthesis item
Part successfully synthesizes 1- acetyl-1-chlorcyclopropanes, and the phase transfer catalyst of higher price, product need not be added in reaction system
Aftertreatment technology is very simple and easy to do, and beneficial to industrialized production, while product yield, more than 82%, solvent separation yield surpasses
Cross 76%, hence it is evident that higher than contrast test.
Claims (7)
1. a kind of synthetic method of improved 1- acetyl-1-chlorcyclopropanes, comprises the following steps：
A, inorganic base and organic solvent are mixed, under stirring condition, is heated to certain temperature；
B, step a temperature is maintained, to add raw material 3, bis- chloro- 2- of 5- into the reaction solution of step a in batches or in a manner of dropwise addition
Pentanone；
C, after being added dropwise to complete, continue to keep thermotonus 0.5-10h；
D, 20-30 DEG C is cooled to after the completion of reaction, filters, takes filtrate；
E, by filtrate rectifying, first recycling design continues rectifying and obtains product；
Organic solvent refers to acetonitrile, benzene,toluene,xylene, dichloromethane, chloroform, four chlorinations wherein described in step a
Carbon, dichloroethanes, ethyl acetate, methyl acetate, ether, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, petroleum ether,
One or more in pentane, n-hexane, hexamethylene, heptane.
2. synthetic method according to claim 1, it is characterised in that the organic solvent is selected from acetonitrile, toluene, acetic acid second
One or more in ester.
3. synthetic method according to claim 1, it is characterised in that be heated to certain temperature described in step a, refer to add
Heat is to 30-110 DEG C.
4. synthetic method according to claim 1, it is characterised in that inorganic base refers to carbonate, carbonic acid described in step a
One or more in hydrogen salt.
5. synthetic method according to claim 4, it is characterised in that the preferred sodium carbonate of the inorganic salts, potassium carbonate, carbonic acid
One or more in hydrogen sodium, saleratus.
6. synthetic method according to claim 1, it is characterised in that the inorganic base and raw material 3,5- Dichloro-2-pentanones
Molal weight ratio is 1:1~3:1；It is preferred that 1.5:1.
7. synthetic method according to claim 1, it is characterised in that in step e, continuing rectifying condition is：Pressure 0.01-
0.15MPa, temperature are 80-120 DEG C, preferably 100 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072437A (en) * | 2021-03-08 | 2021-07-06 | 京博农化科技有限公司 | Method for synthesizing prothioconazole intermediate 1- (1-chlorocyclopropyl) ethanone |
| CN114478216A (en) * | 2020-11-13 | 2022-05-13 | 辽宁众辉生物科技有限公司 | Novel synthesis method of 1-acetyl-1-chlorocyclopropane |
| CN115010587A (en) * | 2022-07-15 | 2022-09-06 | 辽宁众辉生物科技有限公司 | Clean synthesis method of 1-acetyl-1-chlorocyclopropane |
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| CN1942421A (en) * | 2004-04-06 | 2007-04-04 | 拜尔农作物科学有限合伙人公司 | Method of preparing 1-acetyl-1-chlorcyclopropane |
| CN104151149A (en) * | 2014-08-07 | 2014-11-19 | 西安近代化学研究所 | Synthetic method for 1-acetyl-1-cyclopropane chloride |
| CN104292089A (en) * | 2014-09-30 | 2015-01-21 | 大连九信生物化工科技有限公司 | Synthetic process of 1-chloro-cyclopropanecarbonyl chloride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478216A (en) * | 2020-11-13 | 2022-05-13 | 辽宁众辉生物科技有限公司 | Novel synthesis method of 1-acetyl-1-chlorocyclopropane |
| WO2022100711A1 (en) * | 2020-11-13 | 2022-05-19 | 辽宁众辉生物科技有限公司 | Novel synthetic method for 1-acetyl-1-chlorocyclopropane |
| CN113072437A (en) * | 2021-03-08 | 2021-07-06 | 京博农化科技有限公司 | Method for synthesizing prothioconazole intermediate 1- (1-chlorocyclopropyl) ethanone |
| CN115010587A (en) * | 2022-07-15 | 2022-09-06 | 辽宁众辉生物科技有限公司 | Clean synthesis method of 1-acetyl-1-chlorocyclopropane |
| CN115010587B (en) * | 2022-07-15 | 2024-04-30 | 辽宁众辉生物科技有限公司 | Clean 1-acetyl-1-chlorocyclopropane synthesis method |
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