阅读说明：本技术 一种2,6-二甲基-1-茚酮的合成方法 (Synthesis method of 2, 6-dimethyl-1-indanone ) 是由 周芙蓉 王中洋 刘海静 高欢 崔凯凯 左茂辉 李金鸿 于 2020-07-13 设计创作，主要内容包括：本发明属于化学合成领域,涉及一种2,6-二甲基-1-茚酮的合成方法,以间甲基苯甲酰氯和丙烯为原料,在三氯化铝催化下先经傅克酰基化,再经傅克烷基化反应合成目标产物2,6-二甲基-1-茚满酮。该方法合成路线短,总收率高,过程中产生的含铝废水可用来制作絮凝剂,路线整体清洁环保,对环境污染小,适合工业化生产。(The invention belongs to the field of chemical synthesis, and relates to a method for synthesizing 2, 6-dimethyl-1-indanone, which comprises the steps of taking m-methyl benzoyl chloride and propylene as raw materials, carrying out Friedel-crafts acylation under the catalysis of aluminum trichloride, and then carrying out Friedel-crafts alkylation reaction to synthesize a target product 2, 6-dimethyl-1-indanone. The method has the advantages of short synthetic route, high total yield, capability of producing the flocculant from the aluminum-containing wastewater generated in the process, clean and environment-friendly route, low environmental pollution and suitability for industrial production.)

1. A synthetic method of 2, 6-dimethyl-1-indanone is characterized by comprising the following steps: taking m-methyl benzoyl chloride and propylene as raw materials, synthesizing a target product 2, 6-dimethyl-1-indanone through Friedel-crafts acylation under the catalysis of aluminum trichloride and then Friedel-crafts alkylation reaction, wherein the reaction equation is as follows:

2. the method for synthesizing 2, 6-dimethyl-1-indanone according to claim 1, which is characterized in that:

the method comprises the following specific steps:

(1) 1, 2-dichloroethane, m-methylbenzoyl chloride and a Friedel-crafts acylation catalyst aluminum trichloride 1 are sequentially added into a clean reaction bottle at room temperature;

(2) cooling to 0 ℃, starting to introduce propylene gas for reaction for 6 hours, sampling and detecting in the period, and ending the reaction when the methyl benzoyl chloride in the middle of the system is less than or equal to 0.5 percent;

(3) after the reaction is finished, 1, 2-dichloroethane is distilled out;

(4) adding 0.5 equivalent of Friedel-crafts alkylation catalyst aluminum trichloride 2, heating to 80 ℃ and reacting for 4 hours;

(5) after the reaction is finished, dropwise adding the reaction liquid into ice water, and keeping the temperature at-5-0 ℃ for 0.5 h;

(6) performing suction filtration, adding water into a filter cake for leaching until the pH value is about 7, adding methanol and activated carbon into the filter cake, and heating to reflux;

(7) refluxing and decolorizing for 0.5h, cooling to 50 ℃, and performing hot filtration;

(8) the filtrate is decompressed at normal pressure to dissolve out 50 percent of methanol, and is cooled and crystallized;

(9) cooling to 20 ℃, carrying out suction filtration, and drying at 70 ℃ to obtain a target product 2, 6-dimethyl-1-indanone;

in the reaction step, the mass ratio of the m-methyl benzoyl chloride to the 1, 2-dichloroethane is 1: 3-5;

the mol ratio of the m-methyl benzoyl chloride to the aluminum trichloride 1 is 1: 1.05-2;

the mol ratio of the m-methyl benzoyl chloride to the propylene is 1: 1.2-1.5;

the molar ratio of the intermediate methyl benzoyl chloride to the aluminum trichloride 2 in the step (4) is 1: 0.5.

3. The method for synthesizing 2, 6-dimethyl-1-indanone according to claim 2, which is characterized in that: the mass ratio of the m-methyl benzoyl chloride to the ice water is 1: 5-10; the mass ratio of the m-methyl benzoyl chloride to the methanol is 1: 2; the mass ratio of the m-methyl benzoyl chloride to the active carbon is 1: 0.2.

Technical Field

The invention relates to the field of chemical synthesis, and particularly provides a synthesis method of 2, 6-dimethyl-1-indanone.

Background

The triazine indoxacarb with the chemical name of N- [ (1R,2S) -2, 3-dihydro-2, 6 dimethyl-1H-indene-1-yl ] -6- [ (1RS) -1-fluoroethyl ] -1,3, 5-triazine-2, 4-diamine is a triazine herbicide developed by Germany Bayer company, is mainly used for preventing and killing annual weeds (such as crabgrass, eleusine indica, poa pratensis and the like) in lawns, flowers and vegetations and 65 other gramineous weeds and broadleaf weeds, and has the advantages of broad-spectrum weed resistance, long pesticide effect time, low dosage, environmental protection and the like.

The 2, 6-dimethyl-1-indanone is an important raw material of triazinyl indene amine, and the main synthetic route at present is to prepare the triazinyl indene amine by using p-methyl benzyl chloride as a raw material through four steps of condensation, alkaline hydrolysis, acylation and cyclization, and the steps are as follows:

the method has the greatest advantages of easily obtained raw materials, simple reaction, long route, more three wastes and difficult wastewater treatment, and greatly limits the application of the route.

Therefore, the preparation method of the 2, 6-dimethyl-1-indanone, which is more environment-friendly and simpler in process, has great significance on the indamine triazine.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for synthesizing 2, 6-dimethyl-1-indanone, which takes m-methyl benzoyl chloride and propylene as raw materials, and synthesizes a target product 2, 6-dimethyl-1-indanone through Friedel-crafts alkylation reaction after Friedel-crafts acylation under the catalysis of aluminum trichloride. The method has the advantages of short synthetic route, high total yield, capability of producing the flocculant from the aluminum-containing wastewater generated in the process, clean and environment-friendly route, low environmental pollution and suitability for industrial production. The content of the target product synthesized by the preparation method is more than 98 percent, and the total yield is more than 80 percent. The whole route is divided into two steps, and the aluminum-containing waste water can be used for recovering and preparing the flocculating agent.

The specific technical scheme of the invention is as follows:

a method for synthesizing 2, 6-dimethyl-1-indanone is shown as the following formula:

the method comprises the following specific steps:

(1) 1, 2-dichloroethane, m-methylbenzoyl chloride and a Friedel-crafts acylation catalyst aluminum trichloride 1 are sequentially added into a clean reaction bottle at room temperature;

(2) cooling to 0 ℃, starting to introduce propylene gas for reaction for 6 hours, sampling and detecting in the period, and ending the reaction when the methyl benzoyl chloride in the middle of the system is less than or equal to 0.5 percent;

(3) after the reaction is finished, 1, 2-dichloroethane is distilled out;

(4) adding 0.5 equivalent of Friedel-crafts alkylation catalyst aluminum trichloride 2, heating to 80 ℃ and reacting for 4 hours;

(5) after the reaction is finished, dropwise adding the reaction liquid into ice water, and keeping the temperature at-5-0 ℃ for 0.5 h;

(6) performing suction filtration, adding water into a filter cake for leaching until the pH value is about 7, adding methanol and activated carbon into the filter cake, and heating to reflux;

(7) refluxing and decolorizing for 0.5h, cooling to 50 ℃, and performing hot filtration;

(8) the filtrate is decompressed at normal pressure to dissolve out 50 percent of methanol, and is cooled and crystallized;

(9) cooling to 20 ℃, carrying out suction filtration, and drying at 70 ℃ to obtain a target product 2, 6-dimethyl-1-indanone;

in the reaction step, the mass ratio of the m-methyl benzoyl chloride to the 1, 2-dichloroethane is 1: 3-5;

the mol ratio of the m-methyl benzoyl chloride to the aluminum trichloride 1 is 1: 1.05-2;

the mol ratio of the m-methyl benzoyl chloride to the propylene is 1: 1.2-1.5;

the molar ratio of the intermediate methyl benzoyl chloride to the aluminum trichloride 2 in the step (4) is 1: 0.5;

in the reaction, the aluminum trichloride is used as a catalyst for Friedel-crafts acylation and Friedel-crafts alkylation, so that the difference is that in the process of evaporating 1, 2-dichloroethane after the reaction in the step (3), because the aluminum trichloride is easy to sublimate, a part of the aluminum trichloride is lost in the process, and therefore the aluminum trichloride needs to be supplemented before alkylation, the aluminum trichloride is labeled as aluminum trichloride 1 and aluminum trichloride 2, and the other meanings do not exist; the dosage of the aluminum trichloride 2 is calculated on the basis of the dosage of the aluminum trichloride 1, and the inventor thinks that the best catalytic effect can be achieved when the aluminum trichloride is added according to the dosage;

the step 8 of removing and dissolving out 50% of methanol at normal pressure in advance is to avoid the problem that a large amount of methanol is easy to cause the reduction of the crystallization yield in the later period and simultaneously reduce the energy consumption of crystallization;

the molar ratio of the m-methylbenzoyl chloride to propylene is controlled within the above range because too little raw material is not completely reacted and too much impurities are generated; the micro positive pressure is kept in the reaction process, the aeration rate is adjusted during the general operation, and the complete reaction can be ensured by continuously aerating for 6 hours under the condition of ensuring the dosage proportion.

The mass ratio of the m-methyl benzoyl chloride to the ice water is 1: 5-10;

the mass ratio of the m-methyl benzoyl chloride to the methanol is 1: 2;

the mass ratio of the m-methyl benzoyl chloride to the active carbon is 1: 0.2.

In the step (6), a large amount of filtrate is generated by suction filtration, the filtrate contains a large amount of aluminum elements, and for recycling, the filtrate is simply processed to prepare PAC aqueous solution which is used as a flocculating agent for sewage treatment; the following means can be specifically adopted but not limited to: adding excessive sodium hydroxide solution into partial wastewater to prepare sodium metaaluminate, then dropwise adding the sodium metaaluminate into the original wastewater, adjusting the pH of the whole wastewater to be about 3, and generating PAC aqueous solution after conventional high-temperature heat preservation, wherein the method is a common preparation method of the PAC aqueous solution;

in addition, the filter cake is leached by adding water until the pH value is 7, and the generated leaching water can be reused because the leaching water only contains a small amount of aluminum trichloride and can be used for quenching in the next batch after being collected, so that the water consumption of the whole reaction is reduced;

in conclusion, the method provided by the invention has the advantages of short synthetic route and high total yield, the aluminum-containing wastewater generated in the process can be used for preparing the flocculating agent, the route is integrally clean and environment-friendly, the environmental pollution is small, and the method is suitable for industrial production. The content of the target product synthesized by the preparation method is more than 98 percent, and the total yield is more than 80 percent. The whole route is divided into two steps, and the aluminum-containing waste water can be used for recovering and preparing the flocculating agent

Detailed Description

The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.