Preparation method of dicarbonyl cyclopentadienyl cobalt

Abstract

The invention provides a preparation method of dicarbonyl cyclopentadienyl cobalt, which comprises the following steps: adding cobalt salt, a reducing agent, methyl formate and a catalyst into a high-pressure reaction kettle, keeping the reaction kettle in an inert gas atmosphere, and heating and stirring; cooling the high-pressure reaction kettle to room temperature, discharging gas, filtering reaction liquid, and putting filtrate into a normal-pressure reaction device in an inert gas atmosphere; and adding a cyclopentadiene monomer into the normal-pressure reaction device, carrying out heating reaction, filtering after the reaction is finished, and carrying out post-treatment on the obtained filtrate to obtain a dicarbonyl cyclopentadienyl cobalt crude product. The operation risk is reduced, the operation is simple, and the synthesis efficiency is high; cheap and easily available cobalt salt is used as a raw material, and a relatively cheap catalyst is used, so that the synthesis cost is low, and the method is suitable for industrial large-scale popularization and application.

Description

Technical Field

[0001] The present invention relates to the field of metal organic source synthesis, and particularly to a method for preparing dicarbonyl cyclopentadienyl cobalt. Background Art

[0002] Dicarbonyl cyclopentadienyl cobalt is mainly used as a metal organic precursor in chip manufacturing. Through chemical vapor deposition (CVD) or atomic layer deposition (ALD) techniques, it is used to deposit high-purity and high-performance cobalt thin films. These cobalt thin films can be used to manufacture conductive layers, diffusion barrier layers, hard mask materials, and magnetic components, etc. They have excellent electromigration resistance, thermal stability, and electrical characteristics, and can significantly improve the performance and reliability of chips. They are key materials indispensable in modern semiconductor manufacturing.

[0003] CN117126210A discloses a method for synthesizing dicarbonyl cyclopentadienyl cobalt, which includes the following steps: Under the protection of an inert gas, add the raw material cobalt octacarbonyl and tetrahydrofuran solvent to a reaction flask, set up an atmospheric reflux device, and start stirring; drop the tetrahydrofuran solution of sodium cyclopentadienyl into the reaction flask. After the dropping is completed, stir and react at 70-80 °C for 6-10 h; after the stirring reflux ends, first distill the solvent tetrahydrofuran under atmospheric pressure; then change to a vacuum distillation device and distill under reduced pressure to obtain the crude product of dicarbonyl cyclopentadienyl cobalt; the obtained crude product of dicarbonyl cyclopentadienyl cobalt is subjected to vacuum rectification to obtain the finished product of dicarbonyl cyclopentadienyl cobalt. Although its preparation method has concise operation steps and short time consumption, cobalt octacarbonyl is expensive, the synthesis cost is high, and cobalt octacarbonyl is sensitive to air and not easy to store.

[0004] In the existing technologies for synthesizing dicarbonyl cyclopentadienyl cobalt, cobalt octacarbonyl is mainly used as the cobalt source. Although the operation is simple and the time consumption is short, cobalt octacarbonyl is expensive and sensitive and not easy to store, resulting in a high synthesis cost; among them, cobalt octacarbonyl is mainly prepared by cobalt salts and syngas (CO, H2) under high temperature and high pressure conditions in an inert solvent, resulting in problems such as high operating conditions, complex production processes, and safety risks in the synthesis process.

[0005] In view of this, it is necessary to develop a method for preparing dicarbonyl cyclopentadienyl cobalt using inexpensive and easily available cobalt salts as the cobalt source, with simple operation, low safety risk, and low synthesis cost. Summary of the Invention

[0006] The present invention provides a method for preparing dicarbonyl cyclopentadienyl cobalt, which solves the problems of high synthesis cost, complex operation, or high safety risk in the prior art.

[0007] The technical solution of the present invention is realized as follows: A method for preparing dicarbonyl cyclopentadienyl cobalt, and its specific scheme is as follows: Add cobalt salt, reducing agent, methyl formate and catalyst into a high-pressure reactor, and make the atmosphere in the reactor an inert gas atmosphere, then heat and stir; afterwards, the high-pressure reactor is cooled to room temperature, the gas is released, the reaction liquid is filtered, and the filtrate is put into an atmospheric-pressure reaction device with an inert gas atmosphere; Add cyclopentadiene monomer into the atmospheric-pressure reaction device, heat and react, filter after the reaction ends, and the obtained filtrate is post-treated to obtain crude dicarbonylcyclopentadienyl cobalt.

[0008] In some embodiments, the cobalt salt is one of cobalt iodide, cobalt sulfide, cobalt chloride, cobalt sulfate, cobalt acetate. Preferably, it is cobalt iodide.

[0009] In some embodiments, the reducing agent is copper, zinc or manganese. Preferably, it is zinc.

[0010] In some embodiments, the molar ratio of the amount of the cobalt salt to the reducing agent is 1:2.1 - 3.0. The preferred molar ratio is 1:2.2 - 2.4.

[0011] In some embodiments, the methyl formate is replaced with 2,4,6-trichlorophenyl formate or diethyl oxalate. Preferably, it is methyl formate, and the concentration is 0.1 M.

[0012] In some embodiments, the catalyst is [RuCl2(PPh3)3], PdCl2(PPh3)2 or Pd(OAc)2. Preferably, it is [RuCl2(PPh3)3], and the amount used is 0.25 - 0.8 mol%.

[0013] In some embodiments, the molar ratio of the amount of the cobalt salt to the cyclopentadiene monomer is 1:2.5 - 4. The preferred molar ratio is 1:2.5 - 2.8.

[0014] In some embodiments, the filtration process uses a sand core filtration device.

[0015] In some embodiments, the post-treatment is carried out by vacuum distillation.

[0016] In some embodiments, the vacuum distillation removes the front and rear fractions according to the proportion of 3 - 5% of the content of dicarbonylcyclopentadienyl cobalt, and the middle fraction obtained is the crude dicarbonylcyclopentadienyl cobalt.

[0017] In some embodiments, the crude dicarbonylcyclopentadienyl cobalt is rectified to obtain pure dicarbonylcyclopentadienyl cobalt.

[0018] In some embodiments, the temperature in the heating and stirring of the high-pressure reactor is 100 - 150 °C, and the preferred temperature is 120 °C.

[0019] In some embodiments, the temperature in the heating and stirring of the atmospheric pressure reaction device is 50-100 °C, and the preferred temperature is 60 °C.

[0020] In some embodiments, the heating and stirring time of the high-pressure reaction kettle is 6-8 hours.

[0021] In some embodiments, the cobalt salt is cobalt iodide, and the dosage is 20.8 grams; the reducing agent is zinc granules, and the dosage is 9.1 grams; the catalyst is [RuCl2(PPh3)3], and the dosage is 0.32 grams, and the dosage of methyl formate is 43 mL.

[0022] The present invention has the following beneficial effects compared with the prior art: The present invention uses methyl formate, 2,4,6-trichlorophenyl formate or diethyl oxalate to replace carbon monoxide, reducing the operation risk. At the same time, the operation is simple and the synthesis efficiency is high; it avoids the problems of carbon monoxide being flammable, toxic, environmentally unfriendly, and difficult to handle and store; The present invention uses inexpensive and easily available cobalt salt as a raw material, as well as a relatively inexpensive catalyst, with low synthesis cost, and is suitable for large-scale industrial promotion and application; (3) The catalyst used in the present invention can also promote the redox reaction between the cobalt salt and copper, promoting the reaction effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0024] Figure 1 1H NMR spectrum of cobalt cyclopentadienyl dicarbonyl prepared in Example 1.

[0025] Figure 2 13C NMR spectrum of cobalt cyclopentadienyl dicarbonyl prepared in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0027] The reagents or equipment used in the following examples are all commercially available.

[0028] Example 1 Add 20.8 g of cobalt iodide, 8.9 g of 200-mesh copper powder, 0.16 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and make the reactor under an inert gas atmosphere; after the reactor is sealed, turn on the heating device of the reactor, set the temperature to 150 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 100 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then, pure cyclopentadienylcobalt dicarbonyl is obtained through rectification.

[0029] The reaction formula of the above process is as follows:

[0030] The filtration process therein uses a sand core filtration device.

[0031] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 79%.

[0032] Example 2 Add 20.8 g of cobalt iodide, 8.9 g of 200-mesh copper powder, 0.16 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and make the reactor under an inert gas atmosphere; after the reactor is sealed, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then, pure cyclopentadienylcobalt dicarbonyl is obtained through rectification.

[0033] The reaction formula of the above process is as follows:

[0034] The filtration process therein uses a sand core filtration device.

[0035] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 82%.

[0036] Example 3 Add 20.8 g of cobalt iodide, 9.1 g of zinc granules, 0.16 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the equipment. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain the pure product of cyclopentadienylcobalt dicarbonyl by rectification.

[0037] The reaction equation of the above process is as follows:

[0038] The sand core filtration device is used for the filtration process therein.

[0039] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 88%.

[0040] Example 4 Add 20.8 g of cobalt iodide, 7.7 g of 200-mesh manganese powder, 0.16 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the equipment. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain the pure product of cyclopentadienylcobalt dicarbonyl by rectification.

[0041] The reaction equation of the above process is as follows:

[0042] The sand core filtration device is used for the filtration process therein.

[0043] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 85%.

[0044] Example 5 Add 20.8 g of cobalt iodide, 9.1 g of zinc granules, 0.32 g of [RuCl2(PPh3)3], and 43 mL of methyl formate to a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then, pure cyclopentadienylcobalt dicarbonyl is obtained by rectification.

[0045] The reaction formula for the above process is as follows:

[0046] The filtration process uses a sand core filtration device.

[0047] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 93%.

[0048] Example 6 Add 6.1 g of cobalt sulfide, 9.1 g of zinc granules, 0.32 g of [RuCl2(PPh3)3], and 43 mL of methyl formate to a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then, pure cyclopentadienylcobalt dicarbonyl is obtained by rectification.

[0049] The reaction formula for the above process is as follows:

[0050] The filtration process uses a sand core filtration device.

[0051] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 84%.

[0052] Example 7 Add 11.8 g of cobalt acetate, 9.1 g of zinc granules, 0.32 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain a pure product of cyclopentadienylcobalt dicarbonyl by rectification.

[0053] The reaction formula of the above process is as follows:

[0054] The filtration process uses a sand core filtration device.

[0055] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 76%.

[0056] Example 8 Add 20.8 g of cobalt iodide, 9.1 g of zinc granules, 0.32 g of [RuCl2(PPh3)3], and 43 mL of methyl formate into a high-pressure reactor, and keep the reactor under an inert gas atmosphere; after sealing the reactor, turn on the heating device of the reactor, set the temperature to 100 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 50 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain a pure product of cyclopentadienylcobalt dicarbonyl by rectification.

[0057] The reaction formula of the above process is as follows:

[0058] The filtration process uses a sand core filtration device.

[0059] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 89%.

[0060] Example 9 Add 20.8 g of cobalt iodide, 9.1 g of zinc granules, 0.23 g of PdCl2(PPh3)2, and 43 mL of methyl formate into a high-pressure reactor, and make the reactor under an inert gas atmosphere; after the reactor is sealed, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain the pure product of cyclopentadienylcobalt dicarbonyl through rectification.

[0061] The reaction formula of the above process is as follows:

[0062] The filtration process uses a sand core filtration device.

[0063] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 80%.

[0064] Example 10 Add 20.8 g of cobalt iodide, 9.1 g of zinc granules, 0.32 g of [RuCl2(PPh3)3], and 43 mL of 2,4,6-trichlorophenyl formate into a high-pressure reactor, and make the reactor under an inert gas atmosphere; after the reactor is sealed, turn on the heating device of the reactor, set the temperature to 120 °C, and at the same time turn on the stirring inside the device. After 6 hours, cool down; cool down to room temperature, release the gas in the reactor, filter the reaction solution, and put the filtrate into an atmospheric-pressure reaction device under an inert gas atmosphere, and add 2.65 g of cyclopentadiene; stir at 60 °C for 48 hours; after the reaction is completed, filter, and the obtained filtrate is subjected to vacuum distillation to obtain a crude product of cyclopentadienylcobalt dicarbonyl; then obtain the pure product of cyclopentadienylcobalt dicarbonyl through rectification.

[0065] The reaction formula of the above process is as follows:

[0066] The filtration process uses a sand core filtration device.

[0067] The yield of cyclopentadienylcobalt dicarbonyl synthesized in this experiment is 85%.

[0068] The comparison components are detailed in the following table: .

[0069] In summary, when using 20.8 grams of cobalt iodide, 9.1 grams of zinc granules, 0.32 grams of [RuCl2(PPh3)3], and 43 mL of methyl formate, the yield reaches 93%, which is the best ratio.

[0070] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing dicarbonyl cyclopentadienyl cobalt, characterized in that: include: Adding cobalt salt, reducing agent, methyl formate and catalyst into a high-pressure reactor, and making the reactor into an inert gas atmosphere, heating and stirring; then cooling the high-pressure reactor to room temperature, releasing gas, filtering the reaction liquid, and putting the filtrate into a normal pressure reaction device in an inert gas atmosphere; The cyclopentadiene monomer is added into the normal pressure reaction device, heated for reaction, filtered after the reaction is completed, and the obtained filtrate is post-treated to obtain a crude dicarbonyl cyclopentadienyl cobalt product.

2. The method for preparing cobalt dicarbonyl cyclopentadienyl according to claim 1, characterized in that: The cobalt salt is one of cobalt iodide, cobalt sulfide, cobalt chloride, cobalt sulfate and cobalt acetate.

3. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The reducing agent is copper, zinc or manganese.

4. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The molar ratio of the cobalt salt to the reducing agent is 1:2.1-3.

0.

5. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The methyl formate is replaced by 2,4,6-trichlorophenyl formate or diethyl oxalate.

6. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The catalyst is [RuCl2(PPh3)3], PdCl2(PPh3)2 or Pd(OAc)2.

7. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The molar ratio of the cobalt salt to the cyclopentadiene monomer is 1:2.5-4.

0.

8. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The filtering process adopts a sand core filtering device.

9. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The temperature of the high-pressure reactor during heating and stirring is 100-150°C.

10. The method for preparing dicarbonyl cyclopentadienyl cobalt according to claim 1, characterized in that: The temperature of the normal pressure reaction device during heating and stirring is 50-100°C.

Images