Synthesis method of cartosin

Abstract

The invention discloses a synthesis method of Cantocin, which comprises the following steps: taking ferrocene as a raw material, carrying out acylation reaction in the presence of an acylation reagent and a catalyst to obtain acetylferrocene, then carrying out reduction reaction on the acetylferrocene and activated zinc powder under the catalytic action of hydrochloric acid to obtain ethylferrocene, and then carrying out condensation reaction on the ethylferrocene to obtain the Cantocin. And purifying through an organic reagent to obtain the cartosin. According to the method, ferrocene is used as a raw material to synthesize the cartosin through acylation, reduction reaction and condensation reaction, a solvent-free reaction is adopted in the first-step acylation reaction, generation of organic waste liquid is reduced, pollution caused by existing reducing agent zinc amalgam waste liquid is completely eradicated, aftertreatment is simpler, the yield is increased, the synthesis time is saved, and the method is suitable for industrial production. The problems of low yield, low purity and long treatment process of the existing method are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing catocten. Background Art

[0002] Ferrocene derivatives are burning rate catalysts for polybutene propellants and have been widely used in various types of propellant formulations. However, the existing ferrocene burning rate catalysts have volatilization, migration, sublimation, low-temperature crystallization and other phenomena to varying degrees, which seriously affect the ballistic performance of the propellant. 2,2-Bis(ethylferrocene)-propane (catocene, codenamed GFP) is a liquid binuclear ferrocene derivative. It is used as a solid propellant burning rate catalyst. It not only has high catalytic efficiency, but also has low volatility and migration. It can also improve the mechanical properties of the propellant and reduce its pressure index. It has gradually replaced the mononuclear ferrocene burning rate catalyst and has become a widely used type of burning rate catalyst. Therefore, it has a good prospect for wide application in hydroxybutyl propellants.

[0003] However, the current synthesis methods of catoctin often have problems such as low yield, low purity, and difficulty in obtaining some catalysts. In addition, the reduction process produces a lot of toxic wastewater, which is relatively troublesome to handle and causes serious environmental pollution. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for synthesizing catoctenes in view of the deficiencies of the above-mentioned prior art. The method uses ferrocene as a raw material to synthesize catoctenes through acylation, reduction reaction and condensation reaction, and adopts a solvent-free reaction in the first acylation reaction, thereby reducing the generation of organic waste liquid and eliminating the pollution caused by the existing reducing agent zinc amalgam waste liquid, making the post-treatment simpler, improving the yield, saving the synthesis time, and solving the problems of low yield, low purity and long processing steps of the existing method.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for synthesizing catocene, characterized in that ferrocene is used as a raw material, an acylation reaction is carried out under the conditions of an acylating agent and a catalyst to obtain acetyl ferrocene, then the acetyl ferrocene is reduced with activated zinc powder under the catalysis of hydrochloric acid to obtain ethyl ferrocene, then the ethyl ferrocene is subjected to a condensation reaction, and catocene is purified by an organic reagent to obtain.

[0006] The above-mentioned method for synthesizing catoctin is characterized in that the method comprises the following steps:

[0007] Step 1, acylation reaction: add an acylating agent and phosphoric acid into a stirred reactor, react for 10 minutes, add ferrocene, heat to 50°C to 65°C and perform acylation reaction for 1h to 2h, then pour the obtained reaction solution into a 10% mass concentration NaOH ice solution for quenching and neutralization, let it stand and filter to obtain acetyl ferrocene;

[0008] Step 2, reduction reaction: add 1,2-dichloroethane and isopropanol to the acetylferrocene raw material obtained in step 1, then add activated zinc powder, then dropwise add hydrochloric acid and maintain at 60°C to 75°C for reduction reaction until the raw material disappears, filter and wash the obtained organic layer with saturated sodium carbonate and water, and dry over anhydrous sodium sulfate to obtain a crude ethylferrocene;

[0009] Step 3, condensation reaction: methanol and concentrated sulfuric acid are added to the crude ethylferrocene raw material obtained in step 2, and then acetone is added dropwise, and the condensation reaction is maintained at 60° C. to 70° C. until the raw material disappears, and then extracted with a mixed solvent of ethyl acetate and petroleum ether, and the obtained organic phase is washed with water and dried over anhydrous sodium sulfate, and the dried product is dissolved and washed with a mixed solvent of mixed alcohol and petroleum ether to obtain catocine.

[0010] The above-mentioned method for synthesizing cartocin is characterized in that the acylating agent in step 1 is acetic anhydride, and the molar ratio of acetic anhydride to ferrocene is 4 to 5:1.

[0011] The above-mentioned method for synthesizing cartocin is characterized in that the time of the acylation reaction in step 1 is 1.5h.

[0012] The above-mentioned method for synthesizing catocene is characterized in that the mass ratio of the activated zinc powder to the acetylferrocene raw material in step 2 is 3 to 5:1, preferably 3:1.

[0013] The above-mentioned method for synthesizing cartocin is characterized in that the volume ratio of 1,2-dichloroethane to isopropanol in step 2 is 10:1.

[0014] The above-mentioned method for synthesizing catoctin is characterized in that the time of the reduction reaction in step 2 is 3 hours.

[0015] The above-mentioned method for synthesizing catoctenes is characterized in that the molar ratio of the crude ethylferrocene raw material to acetone in step 3 is 1:0.5 to 0.55, preferably 1:0.52.

[0016] The above-mentioned method for synthesizing catoctin is characterized in that the acetone addition time in step 3 is 0.5h, the temperature of the condensation reaction is 80°C, and the reaction time is 5h.

[0017] The above-mentioned method for synthesizing catoctin is characterized in that the mixed alcohol in the mixed alcohol and petroleum ether mixed solvent in step 3 is methanol and isopropanol, and the volume ratio of the mixed alcohol to petroleum ether is 5:1.

[0018] Preferably, the volume ratio of ethyl acetate to petroleum ether in the mixed solvent of ethyl acetate and petroleum ether is 1:2; the temperature for dissolving and washing in the mixed solvent of mixed alcohol and petroleum ether is 50° C., and the time is 1 hour.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] 1. The present invention uses ferrocene as a raw material to synthesize catocene through acylation, reduction reaction and condensation reaction. The method comprises the following steps: directly subjecting ferrocene to an acylation reaction in an acylating agent and performing post-treatment to obtain acetylferrocene; then directly adding activated zinc powder to the acetylferrocene for reduction and post-treatment to obtain a crude ethylferrocene; and finally directly adding a condensing agent to the crude ethylferrocene for condensation reaction to obtain catocene. The first step of the acylation reaction adopts a solvent-free reaction, thereby reducing the parameters of the organic waste liquid, eliminating the pollution caused by the existing reducing agent zinc amalgam waste liquid, making the post-treatment simpler, and improving the yield.

[0021] 2. In the reduction reaction and condensation reaction process of the present invention, the product of the previous step is directly used for the reaction without purification, which shortens the synthesis process, saves synthesis time and improves synthesis efficiency.

[0022] The technical solution of the present invention is further described in detail below through embodiments. DETAILED DESCRIPTION

[0023] Example 1

[0024] This embodiment includes the following steps:

[0025] Step 1, acylation reaction: 1.5L acetic anhydride was added to a stirred reactor, 500mL of 85% phosphoric acid was slowly added dropwise, and after reacting for 10min, 750g of 98% ferrocene was added, the temperature was raised to 60°C and the acylation reaction was carried out for 1.5h, and then the obtained reaction solution was poured into 1L of 10% NaOH ice solution for quenching and neutralization, and the reaction solution was allowed to stand and filtered to obtain 900g of acetylferrocene with a yield of 99%;

[0026] Step 2, reduction reaction: add 5L of 1,2-dichloroethane and 500mL of isopropanol to 900g of acetylferrocene raw material obtained in step 1, then add 2.7kg of activated zinc powder, heat to 70°C, then add 2.5L of 36% hydrochloric acid dropwise within 1.5h and maintain at 70°C for reduction reaction for 3h until the raw material disappears, filter and wash the obtained organic layer with saturated sodium carbonate and water, dry over anhydrous sodium sulfate and spin out the solvent to obtain 794g of crude ethylferrocene with a mass purity of more than 97%, and the yield is 95%;

[0027] Step 3, condensation reaction: under N2 protection, 800g of concentrated sulfuric acid with a mass concentration of 98% was added dropwise to 0.8L of methanol within 0.5h and the system temperature was maintained at 0°C, then added to 794g of ethylferrocene crude raw material obtained in step 2, and then 114g of acetone was added dropwise within 0.5h, and the temperature was maintained at 80°C for condensation reaction for 5h until the raw material disappeared, and then extracted with a mixed solvent consisting of 1L of ethyl acetate and 2L of petroleum ether. The obtained organic phase was washed with saturated sodium carbonate solution and water, dried over anhydrous sodium sulfate and the solvent was spun out, and the dried product was dissolved in a mixed solvent of 416mL of methanol, 416mL of isopropanol and 167mL of petroleum ether at 50°C for 1h, cooled to room temperature, and 714g of catocine was isolated with a yield of 82%.

[0028] Example 2

[0029] The difference between this embodiment and embodiment 1 is that the temperature of the acylation reaction in step 1 is 65° C., and 840 g of acetylferrocene is obtained with a yield of 93%.

[0030] Example 3

[0031] The difference between this embodiment and embodiment 1 is that the temperature of the acylation reaction in step 1 is 50° C., and 870 g of acetylferrocene is obtained with a yield of 96.5%.

[0032] Example 4

[0033] The difference between this embodiment and embodiment 1 is that the volume of acetic anhydride in step 1 is 1.35 L, and 890 g of acetylferrocene is obtained with a yield of 98%.

[0034] Example 5

[0035] The difference between this embodiment and embodiment 1 is that the acylation reaction time in step 1 is 1 hour, and 700 g of acetylferrocene is obtained with a yield of 76%.

[0036] Example 6

[0037] The difference between this embodiment and embodiment 1 is that the acylation reaction time in step 1 is 2 hours, and 800 g of acetylferrocene is obtained with a yield of 89%.

[0038] Example 7

[0039] The difference between this embodiment and embodiment 1 is that in step 2, 4.5 kg of activated zinc powder is added, and 4.5 L of concentrated hydrochloric acid is added dropwise to obtain 794 g of crude ethylferrocene with a mass purity of more than 96%, and the yield is 95%.

[0040] Example 8

[0041] The difference between this embodiment and embodiment 1 is that the reaction temperature in step 2 is raised to 75° C., and 790 g of crude ethylferrocene is obtained with a yield of 93.6%.

[0042] Example 9

[0043] The difference between this embodiment and embodiment 1 is that the reaction temperature in step 2 is 60°C, and 750 g of crude ethylferrocene is obtained, with a yield of 88.8%.

[0044] Example 10

[0045] The difference between this embodiment and embodiment 1 is that 121 g of acetone is added dropwise in step 3 to obtain 700 g of catoctin with a yield of 80%.

[0046] Embodiment 11

[0047] The difference between this embodiment and embodiment 1 is that in step 3, the temperature is raised and maintained at 70° C. for condensation reaction to obtain 640 g of catoctin with a yield of 73.7%.

[0048] Example 12

[0049] The difference between this embodiment and embodiment 1 is that in step 3, the dried product is dissolved in a mixed solvent of 416 mL of ethanol, 416 mL of isopropanol and 167 mL of petroleum ether at 50° C. for 1 h, and cooled to room temperature to obtain 700 g of catoctin with a yield of 80%.

[0050] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent change made to the above embodiment according to the technical essence of the invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A method for synthesizing cartocin, characterized in that: Ferrocene is used as a raw material, an acylation reaction is carried out under the conditions of an acylating agent and a catalyst to obtain acetylferrocene, and then the acetylferrocene is reduced with activated zinc powder under the catalysis of hydrochloric acid to obtain ethylferrocene, and then the ethylferrocene is subjected to a condensation reaction, and catocene is purified by an organic reagent to obtain catocene.

2. The method for synthesizing catoctin according to claim 1, characterized in that: The method comprises the following steps: Step 1, acylation reaction: add an acylating agent and phosphoric acid into a stirred reactor, react for 10 minutes, add ferrocene, heat to 50°C to 65°C and perform acylation reaction for 1h to 2h, then pour the obtained reaction solution into a 10% mass concentration NaOH ice solution for quenching and neutralization, let it stand and filter to obtain acetyl ferrocene; Step 2, reduction reaction: add 1,2-dichloroethane and isopropanol to the acetylferrocene raw material obtained in step 1, then add activated zinc powder, then dropwise add hydrochloric acid and maintain at 60°C to 75°C for reduction reaction until the raw material disappears, filter and wash the obtained organic layer with saturated sodium carbonate and water, and dry over anhydrous sodium sulfate to obtain a crude ethylferrocene; Step 3, condensation reaction: methanol and concentrated sulfuric acid are added to the crude ethylferrocene raw material obtained in step 2, and then acetone is added dropwise, and the condensation reaction is maintained at 60° C. to 70° C. until the raw material disappears, and then extracted with a mixed solvent of ethyl acetate and petroleum ether, and the obtained organic phase is washed with water and dried over anhydrous sodium sulfate, and the dried product is dissolved and washed with a mixed solvent of mixed alcohol and petroleum ether to obtain catocine.

3. The method for synthesizing catoctin according to claim 2, characterized in that: The acylating agent in step 1 is acetic anhydride, and the molar ratio of acetic anhydride to ferrocene is 4 to 5:

1.

4. The method for synthesizing catoctin according to claim 2, characterized in that: The acylation reaction time in step 1 is 1.5 h.

5. The method for synthesizing catoctin according to claim 2, characterized in that: The mass ratio of the activated zinc powder to the acetylferrocene raw material in step 2 is 3 to 5:

1.

6. The method for synthesizing catoctin according to claim 2, characterized in that: The volume ratio of 1,2-dichloroethane to isopropanol in step 2 is 10:

1.

7. The method for synthesizing catoctin according to claim 2, characterized in that: The reduction reaction time in step 2 is 3 h.

8. The method for synthesizing catoctin according to claim 2, characterized in that: The molar ratio of the crude ethylferrocene raw material to acetone in step 3 is 1:0.5-0.

55.

9. The method for synthesizing catoctin according to claim 2, characterized in that: The acetone addition time in step 3 is 0.5 h, the condensation reaction temperature is 80° C., and the reaction time is 5 h.

10. The method for synthesizing catoctin according to claim 2, characterized in that: The mixed alcohol in the mixed alcohol and petroleum ether mixed solvent in step 3 is methanol and isopropanol, and the volume ratio of the mixed alcohol to the petroleum ether is 5:1.