CN111808124B - Synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) - Google Patents
Synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) Download PDFInfo
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- CN111808124B CN111808124B CN202010791994.9A CN202010791994A CN111808124B CN 111808124 B CN111808124 B CN 111808124B CN 202010791994 A CN202010791994 A CN 202010791994A CN 111808124 B CN111808124 B CN 111808124B
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- Prior art keywords
- cyclooctadiene
- turbid liquid
- temperature
- dry tetrahydrofuran
- hexafluoroacetylacetone
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- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- AWUDPEKDPFGDOP-ODZAUARKSA-M sodium;(z)-1,1,1,5,5,5-hexafluoro-4-oxopent-2-en-2-olate Chemical compound [Na+].FC(F)(F)C(/[O-])=C/C(=O)C(F)(F)F AWUDPEKDPFGDOP-ODZAUARKSA-M 0.000 claims abstract description 11
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 9
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 10
- 239000012043 crude product Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 5
- 239000012691 Cu precursor Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- SACLCSGWTQYOLP-UHFFFAOYSA-N cycloocta-1,3-diene;hydrochloride Chemical compound Cl.C1CCC=CC=CC1 SACLCSGWTQYOLP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 201000011452 Adrenoleukodystrophy Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 208000010796 X-linked adrenoleukodystrophy Diseases 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 238000002506 high-vacuum sublimation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which comprises the following steps: s1, reacting with cuprous chloride of cyclooctadiene and sodium hexafluoroacetylacetonate as raw materials to obtain yellow turbid liquid; s2, filtering, washing and concentrating the yellow turbid liquid, and recrystallizing the crude product to obtain a bright yellow crystal product. The invention has the advantages of simple synthesis, easy operation of reaction, simple post-treatment, high yield and purity, simplified operation flow, reduced pollution and easy realization of industrialization of products.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I).
Background
With the development of ALD and CVD technologies and the mature industrial application, the demand for high-purity metal-organic precursors is increasing, the variety of the precursors is also increasing, and the metal-organic precursors with different valence states are often required for the same metal to prepare oxide films with different valence states. The metal organic precursors of copper are divided into a bivalent copper precursor and a monovalent copper precursor, which are respectively used for depositing copper oxide and cuprous oxide films, the bivalent copper precursor in the market is various, and the monovalent stable copper precursor is only hexafluoroacetylacetone-cyclooctadiene copper (I).
However, the existing synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) is a one-pot method, cuprous oxide, cyclooctadiene and hexafluoroacetylacetone are added into tetrahydrofuran solution, after the reaction is finished, the reaction is filtered, tetrahydrofuran is concentrated to dryness, ethanol is added for recrystallization and then high-vacuum sublimation purification is carried out, and the method has the following defects: the reaction yield is 30-40%, and the yield is low; the hexafluoroacetylacetone-copper tetrahydrofuran (I) is produced by the reaction, and is required to be sublimated and purified after recrystallization, so that the difficulty is too high.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I).
The invention provides a synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which comprises the following steps:
s1, reacting with cuprous chloride of cyclooctadiene and sodium hexafluoroacetylacetonate as raw materials to obtain yellow turbid liquid;
s2, filtering, washing and concentrating the yellow turbid liquid, and recrystallizing the crude product to obtain a bright yellow crystal product.
Preferably, in S1, adding the cuprous chloride of the cyclooctadiene and the dry tetrahydrofuran into a reaction bottle, uniformly mixing, controlling the temperature at 5-10 ℃, dropwise adding the dry tetrahydrofuran solution of sodium hexafluoroacetylacetonate under continuous stirring, and after the dropwise adding is finished, returning to room temperature, and stirring and reacting for 5-8 hours to obtain a yellow turbid liquid.
Preferably, in S1, sodium hexafluoroacetylacetonate and dry tetrahydrofuran are added into a reaction bottle to be uniformly mixed, the temperature is controlled at 5-10 ℃, a dry tetrahydrofuran solution of cyclooctadiene cuprous chloride is dropwise added under continuous stirring, after the dropwise addition is finished, the reaction is carried out for 5-8 hours after the room temperature is restored, and a yellow turbid liquid is obtained.
Preferably, in S1, the molar ratio of the cuprous cyclooctadiene chloride to the sodium hexafluoroacetylacetonate is 1:1.
Preferably, in S1, the weight to volume ratio (g/L) of the cuprous cyclooctadiene chloride to the dry tetrahydrofuran is 103.6:0.5-1.
Preferably, in S1, the weight to volume ratio (g/L) of sodium hexafluoroacetylacetonate to dry tetrahydrofuran is 115.02:0.5-1.
Preferably, in S2, washing is performed using dry tetrahydrofuran.
Preferably, in S2, after the filtrate is concentrated, dry ethanol is added for heating and recrystallization, the mixture is slowly cooled to 0 ℃ and stirred for 2 to 3 hours, filtered at low temperature, washed by cold ethanol and dried in vacuum for 2 to 3 hours, and a bright yellow crystal product is obtained.
The synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) provided by the invention is simple to operate, the yield is greatly improved, the effective purity of the product is more than 99%, and the metal purity is more than 99.99%; meanwhile, the thermal stability of the product is good, the thermal weight loss rate reaches more than 99 and can be completely volatilized below 200 ℃ through the thermal weight loss TGA curve of the product, and the product has the excellent performance of a metal organic precursor. The invention has the advantages of simple synthesis, easy operation of reaction, simple post-treatment, high yield and purity, simplified operation flow, reduced pollution and easy realization of industrialization of products.
Drawings
FIG. 1 is a synthetic route diagram of a method for synthesizing hexafluoroacetylacetone-cyclooctadiene copper (I) according to the present invention;
FIG. 2 is a nuclear magnetic spectrum of hexafluoroacetylacetone-cyclooctadiene copper (I) synthesized by the synthesis method provided by the invention;
FIG. 3 is a TGA thermogravimetric plot of hexafluoroacetylacetone-cyclooctadiene copper (I) synthesized by the synthesis method of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which comprises the following steps:
s1, reacting with cuprous chloride of cyclooctadiene and sodium hexafluoroacetylacetonate as raw materials to obtain yellow turbid liquid;
s2, filtering, washing and concentrating the yellow turbid liquid, and recrystallizing the crude product to obtain a bright yellow crystal product.
Embodiment two:
a synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which comprises the following steps:
s1, adding 103.6g of cyclooctadiene cuprous chloride (0.5 mol) and 1L of dry tetrahydrofuran into a 3L four-port round bottom reaction bottle, controlling the temperature of an ice water bath to be 5 ℃, dropwise adding 115.02g of sodium hexafluoroacetylacetonate (0.5 mol) into 500ml of dry tetrahydrofuran solution, controlling the temperature to be 5-10 ℃, ending half an hour of dropwise adding, and returning to room temperature and stirring for 6 hours to change the solution into yellow turbid liquid;
s2, filtering the yellow turbid liquid, washing the turbid liquid with 100ml of dry tetrahydrofuran, concentrating the filtrate to dryness, adding 500ml of dry ethanol, heating and recrystallizing, slowly cooling to 0 ℃ and stirring for 2 hours, filtering at low temperature, washing the turbid liquid with 50ml of cold ethanol, and drying the turbid liquid in vacuum at 50 ℃ for two hours to obtain 173.28g of bright yellow crystals with the yield of 88 percent.
Example III
A synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which comprises the following steps:
s1, adding 115.02g of sodium hexafluoroacetylacetonate (0.5 mol) and 1L of dry tetrahydrofuran into a 3L four-port round bottom reaction bottle, controlling the temperature of an ice water bath to be 5 ℃, dropwise adding 103.6g of 500ml of dry tetrahydrofuran solution of cyclooctadiene cuprous chloride (0.5 mol), controlling the temperature to be 5-10 ℃, ending half an hour of dropwise adding, and returning to room temperature and stirring for 6 hours to change the solution into yellow turbid liquid;
s2, filtering the yellow turbid liquid, washing the turbid liquid with 100ml of dry tetrahydrofuran, concentrating the filtrate to dryness, adding 500ml of dry ethanol, heating and recrystallizing, slowly cooling to 0 ℃ and stirring for 2 hours, filtering at low temperature, washing the turbid liquid with 50ml of cold ethanol, and drying the turbid liquid in vacuum at 50 ℃ for two hours to obtain 181.15g of bright yellow crystals with the yield of 92 percent.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (1)
1. A synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I), which is characterized by comprising the following steps:
s1, adding 103.6g of cyclooctadiene cuprous chloride and 1L of dry tetrahydrofuran into a 3L four-port round bottom reaction bottle, controlling the temperature of an ice water bath to be 5 ℃, dropwise adding 115.02g of sodium hexafluoroacetylacetonate in 500ml of dry tetrahydrofuran solution, controlling the temperature to be between 5 and 10 ℃, stopping dropwise adding for half an hour, and returning to room temperature and stirring for 6 hours to change the solution into yellow turbid liquid; or S1, adding 115.02g of sodium hexafluoroacetylacetonate and 1L of dry tetrahydrofuran into a 3L four-port round bottom reaction bottle, controlling the temperature of an ice water bath to be 5 ℃, dropwise adding 500ml of dry tetrahydrofuran solution of 103.6g of cyclooctadiene cuprous chloride, controlling the temperature to be between 5 and 10 ℃, and after half an hour of dropwise adding, returning to room temperature and stirring for 6 hours, so that the solution becomes yellow turbid liquid;
s2, filtering the yellow turbid liquid, washing the turbid liquid with 100ml of dry tetrahydrofuran, concentrating the filtrate to be dry, adding 500ml of dry ethanol, heating for recrystallization, slowly cooling to 0 ℃ and stirring for 2 hours, filtering at a low temperature, washing the turbid liquid with 50ml of cold ethanol, and drying in vacuum at 50 ℃ for two hours to obtain bright yellow crystals.
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| CN202010791994.9A CN111808124B (en) | 2020-08-08 | 2020-08-08 | Synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) |
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| CN202010791994.9A CN111808124B (en) | 2020-08-08 | 2020-08-08 | Synthesis method of hexafluoroacetylacetone-cyclooctadiene copper (I) |
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| CN111808124A CN111808124A (en) | 2020-10-23 |
| CN111808124B true CN111808124B (en) | 2024-04-05 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385005A (en) * | 1981-07-13 | 1983-05-24 | Exxon Research And Engineering Co. | Process for separating unsaturated hydrocarbons using copper or silver complexes with fluorinated diketonates |
| US5663391A (en) * | 1995-03-07 | 1997-09-02 | Tri-Chemical Laboratory, Inc. | Manufacturing process for producing a β copper diketone complex |
-
2020
- 2020-08-08 CN CN202010791994.9A patent/CN111808124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385005A (en) * | 1981-07-13 | 1983-05-24 | Exxon Research And Engineering Co. | Process for separating unsaturated hydrocarbons using copper or silver complexes with fluorinated diketonates |
| US5663391A (en) * | 1995-03-07 | 1997-09-02 | Tri-Chemical Laboratory, Inc. | Manufacturing process for producing a β copper diketone complex |
Non-Patent Citations (2)
| Title |
|---|
| Chi, K.-M.等." Lewis base adducts of 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato-copper(I)".《Inorganic Syntheses》.1996,第31卷第291页. * |
| K.M.CHI等."The chemistry of β-diketonate copper(I) compounds - III. The synthesis of (β-diketonate)Cu(1,5-COD) compounds, the solid state structure and disproportionation of hexafluoroacetylacetonato(1,5-cyclooctadiene)copper(I), (hfac)Cu(1,5-COD)".《Polyhedron》.2001,第10卷(第10期),第2293-2299页. * |
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