CN112457179B - Preparation method of 5-chloro-1-indanone - Google Patents

Preparation method of 5-chloro-1-indanone Download PDF

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CN112457179B
CN112457179B CN202011411621.0A CN202011411621A CN112457179B CN 112457179 B CN112457179 B CN 112457179B CN 202011411621 A CN202011411621 A CN 202011411621A CN 112457179 B CN112457179 B CN 112457179B
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孙立芹
张洪学
姜殿宝
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Fuxin Ruiguang Fluorine Chemistry Co ltd
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Abstract

The invention provides a preparation method of 5-chloro-1-indanone, belonging to the technical field of organic synthesis. With chlorobenzene and 3-chloropropionyl chlorideTaking mixed molten salt and heteropoly acid as catalysts as raw materials, and heating for reaction to obtain 5-chloro-1-indanone; the heteropoly acid is SiO2The phosphotungstic acid is loaded, and the mixed molten salt is selected from any two or three of potassium chloride, sodium chloride and aluminum chloride. The invention controls the feeding temperature and the feeding sequence to ensure that the reaction is carried out at a lower temperature, thereby avoiding the problems of large solid amount, high temperature, violent reaction, large tar amount, raw material carbonization, more three wastes and the like when aluminum trichloride is used as a catalyst, and the yield of the 5-chloro-1-indanone can reach 85 percent.

Description

Preparation method of 5-chloro-1-indanone
Technical Field
The invention belongs to the technical field of synthesis in pharmaceutical and chemical intermediates, and particularly relates to a preparation method of 5-chloro-1-indanone.
Background
5-chloro-1-indanone, 5-chloro-indanone for short, molecular formula C9H7OCl, molecular weight 166.61, CAS 42348-86-7. Is an important intermediate of a new pesticide indoxacarb (with the common name of indoxacarb) of the DuPont company in the United states, and is also an important medical intermediate of medicaments such as benzoyl indole anti-inflammatory medicaments, amino acetyl anticoagulant medicaments and the like. The currently disclosed synthetic routes for 5-chloroindanone are as follows:
1. the synthesis method taking m-chlorocinnamic acid as a raw material comprises the following steps: the route takes m-chloro cinnamic acid as a raw material, obtains m-chloro phenylpropionic acid by hydrogenation, obtains m-chloro phenylpropionyl chloride by chlorination, and finally obtains 5-chloro indanone by cyclization. The method has the defects that selectivity exists during cyclization, a certain proportion of 7-chloro-2, 3-dihydro-1-indanone is formed, and the product is impure and difficult to separate.
2. The synthesis method using p-chlorobenzoyl chloride as a raw material comprises the following steps: the method takes p-chlorobenzoyl chloride as a raw material, obtains 5-chloroketone under certain pressure by catalyzing ethylene with aluminum chloride, and generates 5-chloroindanone by cyclization of a catalyst. The method has the problems that raw materials are not easy to obtain and pressurization is needed in the process of synthesizing the 5-chloroketone, so that the industrial large-scale production is difficult.
3. The synthesis method using 3-chlorobenzyl chloride as raw material comprises the following steps: the route takes 3-chlorobenzyl chloride as an initial raw material, and 5-chlorin indanone is synthesized by 5 steps of nucleophilic substitution, hydrolysis, decarboxylation, acyl chlorination, Friedel-crafts acylation and the like. The method has the advantages of easily obtained raw materials and high product purity, but has the problems of complex synthesis operation, low single-step yield and the like, and is not suitable for industrial production.
4. The synthesis method of chlorobenzene as a raw material has the following reaction formula:
Figure BDA0002815475950000011
this route is in turn catalyzed by different catalysts:
1) 3-chloropropionyl chloride and chlorobenzene are used as raw materials, sulfuric acid is used as a catalyst, and 5-chloroketone is generated by reaction at a certain temperature and time; under the catalysis of concentrated sulfuric acid, cyclizing to generate the product 5-chloro-indanone. The first step is Friedel-crafts acylation reaction, and the yield is up to 90 percent; the second reaction step is a cyclization reaction, and the yield is 55 percent, and the total yield is about 50 percent. The reaction route has high yield and short reaction time, but concentrated sulfuric acid is used as a catalyst, so that the required reaction amount is large, the requirement on equipment is strict, the utilization efficiency is low, the amount of quenched wastewater is large, the waste liquid is difficult to treat, the environmental pollution is serious, and the method is neither economical nor environment-friendly.
2) Reacting 3-chloropropionyl chloride with chlorobenzene at 120 ℃ in the presence of excessive trifluoromethanesulfonic acid as a catalyst to obtain 5-chloroketone with the yield of 45%; 5-chloroketone reacts at 90 ℃ in excess trifluoromethanesulfonic acid as a catalyst to obtain 5-chloroindanone with a yield of 98%. The method uses trifluoromethanesulfonic acid as a catalyst, the trifluoromethanesulfonic acid is expensive and has strong corrosivity, serious burns can be caused, and simultaneously a large amount of trifluoromethanesulfonic acid is difficult to treat and the equipment has high corrosivity.
3) Under the protection of nitrogen, chlorobenzene and 3-chloropropionyl chloride are mixed and cooled to 0 ℃, hydrofluoric acid and boron trifluoride are added as catalysts, and 5-chloroindanone is generated by cyclization under the action of concentrated sulfuric acid. The method has the defects of high energy consumption, large pollution and the like, and has the problems of inconvenient operation, difficult post-treatment and the like.
4) 3-chloropropionyl chloride and chlorobenzene are used as raw materials, aluminum trichloride is used as a catalyst, a molten salt solution is used as a solvent, and a product 5-chloroindanone is generated at a certain temperature. The one-pot method and the fractional step method have the same problems, the reaction temperature is high (150-200 ℃), the using amount of aluminum trichloride is large, the tar content is large, the sublimed aluminum trichloride and product solids are easy to block an exhaust pipeline, potential safety hazards are caused, the yield is low (50-70%), and the color difference of the product is low.
Disclosure of Invention
In order to overcome the technical defects, the invention takes chlorobenzene and 3-chloropropionyl chloride as raw materials, has simple process and easily obtained raw materials through a Friedel-crafts acylation and cyclization reaction route, and has significance for industrial large-scale production, wherein the selection of a catalyst, the feeding mode and the reaction temperature are the key points for the success of the reaction process.
In view of the above, the present invention provides a method for mixing a molten salt and SiO2The supported phosphotungstic acid is used as a catalyst, the using amount of aluminum trichloride is greatly reduced, the reaction process is controlled by adjusting the feeding sequence and the feeding temperature, the reaction temperature is reduced, and the generation of a dehydrochlorination intermediate byproduct, namely 4-chlorophenyl propenone, is reduced, so that the generation of tar is reduced, the yield of a product is improved, and the pressure of acid gas on an absorption system in the post-treatment process is avoided.
The invention provides a preparation method of 5-chloro-1-indanone, which comprises the following steps: chlorobenzene and 3-chlorine-propionyl chloride are used as raw materials, mixed molten salt and heteropoly acid are used as catalysts, and the temperature is raised for reaction to obtain 5-chlorine-1-indanone; the heteropoly acid is SiO2The phosphotungstic acid is loaded, and the mixed molten salt is selected from any two or three of potassium chloride, sodium chloride and aluminum chloride.
The preparation method comprises the following steps:
A. heating heteropoly acid and mixed molten salt to a molten state; B. adding 3-chlorine-propionyl chloride into the system A under a certain temperature, then adding chlorobenzene into the reaction liquid, and carrying out heat preservation reaction to obtain 5-chlorine-1-indanone; C. quenching the reaction solution in the step B in ice water, and filtering; D. and C, recrystallizing the filtered crude product in the step C, decoloring and drying to obtain the 5-chloro-1-indanone. More specifically, the method comprises the following detailed steps:
1) firstly, mixed molten salt of heteropoly acid catalyst and aluminum trichloride is placed in a reaction vessel, and then is heated to a molten state under the condition of stirring and controlling a certain temperature.
Further, the heteropoly acid is SiO2The supported phosphotungstic acid is 20-40%.
Furthermore, the amount of the heteropoly acid is 3-10% of 3-chloropropionyl chloride in terms of phosphotungstic acid, and the heteropoly acid is recycled for five times.
Further, the SiO2Preparation method of supported phosphotungstic acid catalystComprises the following steps: dissolving phosphotungstic acid with distilled water, slowly adding a certain amount of mixture of ethyl orthosilicate and n-butanol dropwise into aqueous solution of phosphotungstic acid, keeping the temperature at 40 deg.C and 80 deg.C for 1h, 2h and 3h respectively, vacuum drying the obtained gel at 45 deg.C for 15h, vacuum drying at 90 deg.C for 3h, washing the gel with warm water at 50 deg.C, and calcining at 240 deg.C for 3h to obtain SiO2And loading a phosphotungstic acid catalyst.
Further, the mixed molten salt consists of 0-15 wt% of potassium chloride, 0-50 wt% of sodium chloride and the balance of aluminum trichloride, wherein the potassium chloride and the sodium chloride are not zero at the same time.
Furthermore, the dosage of the aluminum trichloride is 1 to 1.1 times of the molar weight of the 3-chloropropionyl chloride.
Further, the reaction temperature is 90-120 ℃.
2) Keeping a certain temperature, adding 3-chloro-propionyl chloride into the mixed molten salt in the step 1), then adding chlorobenzene, and carrying out heat preservation reaction to obtain 5-chloro-1-indanone; the structural formula of the 5-chloro-1-indanone is as follows:
Figure BDA0002815475950000031
further, the molar ratio of 3-chloro-propionyl chloride to chlorobenzene was 1: 1.
Further, the reaction temperature is 100-120 ℃, and the reaction heat preservation time is 1-5 hours.
3) And 3) quenching the reaction solution in the step 2) in ice water after the temperature preservation is finished, and filtering.
Furthermore, the amount of the ice water is 5-10 times of that of the aluminum trichloride, the quenching temperature is 0-50 ℃, and the filtering temperature is below 20 ℃.
4) Recrystallizing the crude product filtered out in the step 3) and recovering the supported catalyst. After the filtrate is decolorized, off-white to light yellow crystalline powder which is a pure product of 5-chloro-1-indanone is obtained.
Further, the recrystallization solvent is one of methanol, ethanol, acetone, isopropanol, and the like.
Further, the temperature of recrystallization heat filtration is the reflux temperature of the solvent.
Further, it is characterized byFiltering the hot filtered filter cake with a mixed solvent of dichloromethane, chloroform and toluene, and recovering SiO2And loading a phosphotungstic acid catalyst.
The preparation method provided by the invention has the advantages of simple process, greatly reduced aluminum trichloride consumption, mild conditions, high yield, less three wastes, greatly reduced environmental pollution, low equipment requirement and easy industrial production.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but will not limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A2000 mL jacketed reactor was charged with 338g (3mol) of chlorobenzene, cooled to below 5 ℃ and stirred for 0.5h with 420g (3.15mol) of aluminum trichloride. 381g (3mol) of 3-chloropropionyl chloride is added dropwise, and the addition is finished within 2 h. After the addition, the temperature is raised to 50 ℃, and after the reaction is carried out for 2 hours, the GC controlled reaction raw material is less than or equal to 0.5 percent. 300g of aluminum trichloride, 90g of sodium chloride and 30g of potassium chloride are added into the other jacket kettle, and jacket heat conduction oil is heated to a molten state. And (4) dropwise adding the reaction liquid after heat preservation into the molten salt, wherein the reaction liquid takes 1h, after dropwise adding, heating to 130 ℃, preserving heat for 6h, and finishing the reaction. Adding the reaction liquid into 4000g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering to obtain a black filter cake, adding the filter cake into the reaction kettle, adding 1000g of methanol, heating to reflux, keeping the temperature for 3 hours, carrying out thermal filtration, returning mother liquor to the kettle, heating to be completely dissolved, decoloring and crystallizing by using activated carbon to obtain 368g (2.2mol) of yellow solid, wherein the GC purity is 99.5%, the HPLC purity is 99.2%, and the yield is 73.6%.
Example 2
338g (3mol) of chlorobenzene was added to a jacketed reaction vessel of 2000mL, and then the temperature was lowered to 5 ℃ or lower, followed by addition of 420g (3.15mol) of aluminum trichloride and stirring for 0.5 hour. 381g (3mol) of 3-chloropropionyl chloride is added dropwise, and the addition is finished within 2 h. After the addition, the reaction temperature is raised to 70 ℃, and after the reaction is carried out for 2 hours under the condition of heat preservation, the GC controlled reaction raw material is less than or equal to 0.5 percent. 600g of aluminum trichloride and 260g of sodium chloride are added into the other jacket kettle, jacket heat conduction oil is heated to a molten state, reaction liquid after heat preservation is dripped, the reaction liquid takes 1h, the temperature is raised to 150 ℃ after dripping, heat preservation is carried out for 3h, and the reaction is finished. Adding the reaction liquid into 5000g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 1000g of methanol, heating to reflux, keeping the temperature for 3 hours, carrying out heat filtration, decoloring and crystallizing mother liquor by using activated carbon to obtain 349g (2.09mol) of yellow solid, wherein the GC purity is 99.6%, the HPLC purity is 99.2%, and the yield is 69.8%.
Example 3
1000mL jacketed reaction kettle is added with SiO231.8g of supported phosphotungstic acid catalyst (with the load of 30 percent), 210g of aluminum trichloride, 90g of sodium chloride and 49g of potassium chloride, heating to 90 ℃ in a jacket oil bath, preserving heat for 0.5h, controlling the temperature of a reaction kettle to be 100 plus materials, dropwise adding 190.5g (1.5mol) of 3-chloropropionyl chloride, keeping the temperature for 30 minutes after the dropwise adding is finished, dropwise adding 169g (1.5mol) of chlorobenzene, keeping the temperature for 1h after the dropwise adding is finished, and finishing the reaction by controlling the intermediate to be less than or equal to 0.5 percent in GC after the dropwise adding is finished and the reaction is carried out for 4 hours. Adding the reaction liquid into 1250g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 500g of methanol, heating to reflux, preserving heat for 3 hours, carrying out hot filtration, carrying out hot shuffling on the filter cake with chloroform, filtering, leaching and drying, and recovering the supported catalyst. The methanol mother liquor is returned to the kettle, heated to be completely dissolved, and decolored and crystallized by active carbon to obtain 223g (1.34mol) of off-white solid with the GC purity of 99.7 percent, the HPLC purity of 99.3 percent and the yield of 89.2 percent.
Example 4
1000mL jacketed reaction kettle is added with SiO231.8g of phosphotungstic acid catalyst (with the load of 30 percent), 210g of aluminum trichloride and 90g of sodium chloride are loaded, a jacket oil bath is heated to 100 ℃, the temperature is kept for 0.5h, the temperature of the reaction kettle is controlled to be 110-plus-120 ℃, 190.5g (1.5mol) of 3-chloropropionyl chloride is dripped, the reaction lasts for 2h, the temperature is kept for reaction for 30 min after dripping, 169g (1.5mol) of chlorobenzene is dripped, the reaction lasts for 1h, and after the heat preservation reaction is finished for 3h, the reaction of the GC intermediate is controlled to be less than or equal to 0.5 percent, and the reaction is finished. The reaction feed was added to 1250g of iceHydrolyzing in water, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 500g of methanol, heating to reflux, keeping the temperature for 3 hours, carrying out hot filtration, shuffling the filter cake with chloroform, filtering, leaching and drying, and recovering the supported catalyst. The methanol mother liquor is returned to the kettle, heated to be completely dissolved, and decolored and crystallized by active carbon to obtain 218g (1.31mol) of off-white solid with the GC purity of 99.8 percent, the HPLC purity of 99.4 percent and the yield of 87.2 percent.
Example 5
2000mL jacketed reactor, SiO was added250.13g of a phosphotungstic acid catalyst (with the load of 38 percent) is loaded, 420g of aluminum trichloride and 210g of sodium chloride are loaded, a jacket oil bath is heated to 110 ℃, the temperature is kept for 0.5h, the temperature of the reaction kettle is controlled to be 110-plus-120 ℃, 381g (3mol) of 3-chloropropionyl chloride is dripped, the time is 2.5h, after dripping is finished, 338g (3mol) of chlorobenzene is dripped at the temperature, the time is 1.5h, and after the heat preservation reaction is finished for 3h, the reaction of less than or equal to 0.5 percent of a GC intermediate is finished. Adding the reaction liquid into 2500g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 1000g of methanol, heating to reflux, keeping the temperature for 3 hours, carrying out hot filtration, carrying out hot shuffling on the filter cake with chloroform, filtering, leaching and drying, and recovering the supported catalyst. The methanol mother liquor is returned to the kettle, heated to be completely dissolved, and decolored and crystallized by active carbon to obtain 443g (2.66mol) of off-white solid with the GC purity of 99.6 percent, the HPLC purity of 99.3 percent and the yield of 88.6 percent.
Example 6
2000mL of SiO recycled once is added into a jacketed reaction kettle264g of load phosphotungstic acid catalyst (load capacity is 30%), 420g of aluminum trichloride, 181g of sodium chloride and 99g of potassium chloride, heating to 90 ℃ in a jacket oil bath, preserving heat for 0.5h, controlling the temperature of the reaction kettle to be 105-plus-110 ℃, dropwise adding 381g (3mol) of 3-chloropropionyl chloride, taking 2.5h, preserving heat for 30 min at the temperature after dropwise adding, beginning dropwise adding 338g (3mol) of chlorobenzene, taking 1.5h, and finishing the reaction of controlling the intermediate to be less than or equal to 0.5% by GC after the dropwise adding and preserving heat for reacting for 3.5 h. Adding the reaction liquid into 2500g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 1000g of methanol, heating to reflux, preserving heat for 3 hours, carrying out hot filtration, filteringThe cake was hot shuffled with chloroform, filtered, rinsed and dried, and the supported catalyst was recovered. The methanol mother liquor is returned to the kettle, heated to be completely dissolved, and decolored and crystallized by active carbon to obtain 429.9g (2.58mol) of off-white solid with the GC purity of 99.5 percent, the HPLC purity of 99.2 percent and the yield of 86 percent.
Example 7
2000mL jacketed reactor, SiO recovered five times was added262g of phosphotungstic acid catalyst (with the load of 30 percent) is loaded, 420g of aluminum trichloride, 180g of sodium chloride and 98g of potassium chloride are loaded, a jacket oil bath is heated to 90 ℃, the temperature is kept for 0.5h, the temperature of the reaction kettle is controlled to be 105-plus-110 ℃, 381g (3mol) of 3-chloropropionyl chloride is dripped, the time is 2h, the temperature is kept for 30 min at the temperature after dripping, 338g (3mol) of chlorobenzene is dripped, the time is 2.5h, and after the heat preservation reaction is finished for 5h, the reaction of controlling the intermediate in GC to be less than or equal to 0.5 percent is finished. Adding the reaction liquid into 2500g of ice water for hydrolysis, controlling the temperature of a hydrolysis kettle to be less than or equal to 50 ℃, stirring after dripping, cooling to be below 20 ℃, filtering, adding a filter cake into the reaction kettle, adding 1000g of methanol, heating to reflux, keeping the temperature for 3 hours, carrying out hot filtration, carrying out hot shuffling on the filter cake with chloroform, filtering, leaching and drying, and recovering the supported catalyst. The methanol mother liquor is returned to the kettle and heated to be completely dissolved, and then the light yellow solid 401g (2.41mol) is obtained after the activated carbon decoloration and crystallization, the GC purity is 99.5 percent, the HPLC purity is 99.3 percent, and the yield is 80.2 percent.
Example 8
SiO2Preparation of a supported phosphotungstic acid catalyst:
dissolving 50g of phosphotungstic acid in 200mL of distilled water, slowly dropwise adding 315g of a mixture (volume ratio is 2.5:1) of ethyl orthosilicate and n-butanol into a phosphotungstic acid aqueous solution, respectively preserving heat for 1h, 2h and 3h at room temperature, 40 ℃ and 80 ℃ after the addition is finished, vacuum drying the obtained gel for 15h at 45 ℃, vacuum drying for 3h at 90 ℃, washing the gel with warm water at 50 ℃, and then roasting for 3h at 240 ℃ to obtain SiO2And loading a phosphotungstic acid catalyst.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (7)

1. The preparation method of 5-chloro-1-indanone is characterized by comprising the following steps: A. heating heteropoly acid and mixed molten salt to a molten state; B. adding 3-chlorine-propionyl chloride into the system A under a certain temperature, then adding chlorobenzene into the reaction liquid, and carrying out heat preservation reaction to obtain 5-chlorine-1-indanone; C. quenching the reaction solution in the step B in ice water, and filtering; D. recrystallizing, decoloring and drying the filtered crude product in the step C to obtain 5-chloro-1-indanone; in the step A and the step B, the reaction temperature is 90-120 ℃; in the step A, the heteropoly acid is SiO2 loaded phosphotungstic acid, the mixed molten salt is composed of 0-15 wt% of potassium chloride, 0-50 wt% of sodium chloride and the balance of aluminum trichloride, and the potassium chloride and the sodium chloride are not zero at the same time.
2. The process for preparing 5-chloro-1-indanone according to claim 1, which comprises: the heteropoly acid is a SiO2 supported phosphotungstic acid catalyst, and the loading amount is 20-40%.
3. The process for preparing 5-chloro-1-indanone according to claim 2, which comprises: the dosage of the heteropoly acid is 3-10% of the mass of 3-chloropropionyl chloride calculated by phosphotungstic acid.
4. The process for preparing 5-chloro-1-indanone according to claim 1, which comprises: in the step A, the dosage of the aluminum trichloride is 1 to 1.1 times of the molar weight of the 3-chlorine-propionyl chloride; in the step B, the dosage of the chlorobenzene is 1 time of the molar quantity of the 3-chloropropionyl chloride.
5. The process for preparing 5-chloro-1-indanone according to claim 1, which comprises: in step C, the reaction is quenched by adding ice water at 0-50 deg.C and filtering at a temperature below 20 deg.C.
6. The process for preparing 5-chloro-1-indanone according to claim 1, which comprises: in step D, the solvent for recrystallization heat filtration is methanol, ethanol, acetone or isopropanol.
7. The process for preparing 5-chloro-1-indanone according to claim 1, which comprises: and D, recovering the catalyst, wherein the method for recovering the catalyst comprises the step of filtering and drying the filtered filter cake by using dichloromethane, chloroform or toluene mixed solvent.
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