JP4193631B2 - Process for producing β-diketonato copper complex - Google Patents
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- 150000004699 copper complex Chemical class 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 40
- -1 copper carboxylate Chemical class 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000008346 aqueous phase Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 9
- 239000005750 Copper hydroxide Substances 0.000 description 9
- 229910001956 copper hydroxide Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Description
本発明は、化学気相蒸着法（ＣＶＤ法）により銅あるいは銅含有合金等の金属薄膜または銅酸化物を一構成成分とする複合酸化物薄膜等の銅含有薄膜を形成させる際に銅源として使用されるβ−ジケトナト銅錯体の製造方法に関する。 The present invention provides a copper source for forming a copper-containing thin film such as a metal thin film such as copper or a copper-containing alloy or a composite oxide thin film containing copper oxide as a constituent component by chemical vapor deposition (CVD). The present invention relates to a method for producing a β-diketonato copper complex to be used.
金属銅薄膜の製造に使用される２価のβ−ジケトナト銅錯体としては、ビス（アセチルアセトナト）銅あるいは、ビス（ジピバロイルメタナト）銅がある。ビス（アセチルアセトナト）銅錯体の合成法としては、例えば硝酸銅水溶液にアンモニア水を加え、これとアセチルアセトンを反応させ、沈殿して得られた銅錯体を濾別、水洗、乾燥して、目的の銅錯体を得る方法が知られている（非特許文献１）。しかしながら、固体を濾別する工程を含む方法は、大量製造が要求される工業的観点からは、有利な方法ではない。 Examples of the divalent β-diketonato copper complex used for the production of the metallic copper thin film include bis (acetylacetonato) copper or bis (dipivaloylmethanato) copper. As a method for synthesizing a bis (acetylacetonato) copper complex, for example, aqueous ammonia is added to an aqueous copper nitrate solution, this is reacted with acetylacetone, and the resulting copper complex is separated by filtration, washed with water, dried, A method for obtaining a copper complex of is known (Non-patent Document 1). However, a method including a step of filtering out a solid is not an advantageous method from an industrial viewpoint that requires mass production.
また、特許文献１及び特許文献２に示されるβ−ジケトナト銅錯体の合成では、水酸化銅をトルエンに懸濁させ、β−ジケトンと加熱脱水しながら反応させた後、未反応の水酸化銅を濾別する操作を行っている。この方法では、水酸化銅のトルエンへの溶解性が低いため、固相の存在する不均一系反応であり、反応効率が悪いのに加え未反応の水酸化銅の濾別操作が入るため、工業的製造法としては問題である。また、特許文献３に示されるβ−ジケトナト銅錯体の合成においては、銅源として酢酸銅を使用しているが、生成した固体の銅錯体を濾別法にて得ており、また反応収率も低く、大量生産を考慮した工業的製造方法とは言えないものである。また、特許文献４に記載の銅錯体の合成方法では、塩化銅とβ−ジケトンのカリウム塩を反応させているが、β−ジケトンのカリウム塩合成での煩雑さや塩化銅による不均一反応系を含んだものであり、やはり工業的合成方法とは言えないものであった。 In addition, in the synthesis of β-diketonato copper complexes shown in Patent Document 1 and Patent Document 2, copper hydroxide is suspended in toluene, reacted with β-diketone while heating and dehydrating, and then unreacted copper hydroxide. The operation of filtering is performed. In this method, since the solubility of copper hydroxide in toluene is low, it is a heterogeneous reaction in which a solid phase exists, and since the reaction efficiency is poor, an operation for separating unreacted copper hydroxide is performed. It is a problem as an industrial production method. Moreover, in the synthesis | combination of the beta-diketonato copper complex shown by patent document 3, although the copper acetate is used as a copper source, the produced | generated solid copper complex is obtained by the filtration method, Moreover, reaction yield Therefore, it cannot be said to be an industrial manufacturing method considering mass production. In addition, in the method for synthesizing a copper complex described in Patent Document 4, copper chloride and a potassium salt of β-diketone are reacted, but the complexity in the synthesis of the potassium salt of β-diketone and the heterogeneous reaction system due to copper chloride are reduced. It was included, and was still not an industrial synthesis method.
本発明は、ＣＶＤ法による銅を成分として含む薄膜あるいは酸化銅含有薄膜形成原料として適した、シリルエーテル基を持つβ−ジケトンを配位子とするβ−ジケトナト銅錯体の製造方法の提供を目的とする。具体的には、量産化において障害となる操作である濾別工程を必要とせず、高収率で大量合成が可能な製造方法の提供を目的とする。 An object of the present invention is to provide a method for producing a β-diketonato copper complex having a β-diketone having a silyl ether group as a ligand, which is suitable as a thin film containing copper as a component by CVD or a raw material for forming a copper oxide-containing thin film. And Specifically, an object of the present invention is to provide a production method capable of mass synthesis at a high yield without requiring a filtration step, which is an operation that hinders mass production.
本発明者は、シリルエーテル基を持つβ−ジケトンを配位子とするβ−ジケトナト銅錯体の製造において、固体を含まない液相二相系を使用することおよび本反応での平衡を生成系に移衡させる操作により収率が向上し、前記課題が解決されることを見出し、本発明を完成した。
すなわち本発明は、下記一般式（Ｉ）で表されるβ−ジケトナト銅錯体（式中Ｒ１は、炭素原子数１〜５の直鎖または分枝のアルキル基、Ｒ２は、炭素原子数１〜５の直鎖または分枝のアルキレン基；以下、銅錯体）の製造において、反応系を、一般式（II）で示されるβ−ジケトン（式中Ｒ１は、炭素原子数１〜５の直鎖または分枝のアルキル基、Ｒ２は、炭素原子数１〜５の直鎖または分枝のアルキレン基；以下、β−ジケトン）含有の有機溶媒相と、炭素原子数１〜６の脂肪族カルボン酸（以下、カルボン酸）の２価銅塩（以下、カルボン酸銅）の水溶液相とから構成される二相系とし、反応系に固体が存在しない状態でβ−ジケトンとカルボン酸銅とを反応させことを特徴とする銅錯体の製造方法に関するものである。
In the production of a β-diketonato copper complex having a β-diketone having a silyl ether group as a ligand, the present inventor uses a liquid phase two-phase system containing no solid and generates an equilibrium in this reaction. The present invention has been completed by finding that the yield is improved by the operation of transferring to the solution and the above-mentioned problems are solved.
That is, the present invention provides a β-diketonato copper complex represented by the following general formula (I) (wherein R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, and R 2 is the number of carbon atoms. In the production of a linear or branched alkylene group of 1 to 5; hereinafter referred to as a copper complex), the reaction system is a β-diketone represented by the general formula (II) (wherein R 1 represents 1 to 5 carbon atoms). A linear or branched alkyl group, R 2 is a linear or branched alkylene group having 1 to 5 carbon atoms; hereinafter referred to as a β-diketone), and an organic solvent phase having 1 to 6 carbon atoms It is a two-phase system composed of an aqueous phase of an aliphatic carboxylic acid (hereinafter referred to as carboxylic acid) divalent copper salt (hereinafter referred to as copper carboxylate), and β-diketone and carboxylic acid in the absence of solids in the reaction system The present invention relates to a method for producing a copper complex characterized by reacting with copper.
本発明の好ましい実施態様は、β−ジケトン含有の有機溶媒相とカルボン酸銅水溶液相よりなる液相二相系でβ−ジケトンとカルボン酸銅とを反応させる上記方法において、反応後にカルボン酸銅水溶液相と有機溶媒相とを分液し、有機溶媒相に新たにカルボン酸銅水溶液を添加しβ−ジケトンとカルボン酸銅とを反応を行なわせた後、カルボン酸銅水溶液相と有機溶媒相を分液する一連の操作を一回以上繰り返して加える、銅錯体の製造方法である。 A preferred embodiment of the present invention is the above-described method in which a β-diketone and copper carboxylate are reacted in a liquid phase two-phase system comprising a β-diketone-containing organic solvent phase and a copper carboxylate aqueous solution phase. The aqueous solution phase and the organic solvent phase are separated, a copper carboxylate aqueous solution is newly added to the organic solvent phase, and the β-diketone and copper carboxylate are reacted. This is a method for producing a copper complex, in which a series of operations for separating the liquid is repeated one or more times.
本発明の特に好ましい実施態様は、カルボン酸銅として酢酸銅を使用する方法である。 A particularly preferred embodiment of the present invention is a process using copper acetate as the carboxylate copper.
本発明の銅錯体の製造方法は、固体を含まない液相二相系反応であり、反応後、未反応の固体である銅塩の濾過操作が不要である。また、本反応は平衡反応であることから、副生成物を反応系からの留去操作により、平衡を移衡することにより、高収率で目的物が得られる。すなわち、容易な反応操作性および高収率の点から、工業的製造法として実用的である。 The method for producing a copper complex of the present invention is a liquid phase two-phase reaction that does not contain a solid, and does not require a filtering operation of a copper salt that is an unreacted solid after the reaction. Since this reaction is an equilibrium reaction, the target product can be obtained in high yield by transferring the equilibrium by distilling off the by-products from the reaction system. That is, it is practical as an industrial production method from the viewpoint of easy reaction operability and high yield.
以下で、本発明を詳細に説明する。
本発明の対象となる、前記一般式（Ｉ）で示される、シリルエーテル系のβ−ジケトナト配位子を含む銅錯体の具体的な例としては、たとえば、式（III）から（Ｖ）に示される銅錯体が挙げられる。式（III）で示される銅錯体は、ビス（２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオナト）銅（II）錯体［以下、Ｃｕ(ｓｏｐｄ)２と称す］である。
The present invention is described in detail below.
Specific examples of the copper complex containing the silyl ether-based β-diketonato ligand represented by the general formula (I), which is the subject of the present invention, include, for example, formulas (III) to (V): The copper complex shown is mentioned. The copper complex represented by the formula (III) is a bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadionato) copper (II) complex [hereinafter referred to as Cu (sopd) 2 ]. is there.
本発明は、β−ジケトンとカルボン酸銅とを、β−ジケトンを含む有機溶媒相と、カルボン酸銅水溶液相からなる、固体を含まない二液相系で反応させることを特徴とするが、
本発明で使用される一般式（II）で示されるβ−ジケトンの具体例としては、例えば上記（III）〜（Ｖ）として示される銅錯体の製造にそれぞれ使用される、下記（III’）〜（Ｖ’）に示される、シリルエーテル基を持つβ−ジケトンを挙げることが出来る。
The present invention is characterized in that β-diketone and copper carboxylate are reacted in a two-liquid phase system including a solid solution containing an organic solvent phase containing β-diketone and a copper carboxylate aqueous solution phase,
Specific examples of the β-diketone represented by the general formula (II) used in the present invention include, for example, the following (III ′) respectively used for the production of copper complexes represented by the above (III) to (V): The (beta) -diketone which has a silyl ether group shown by-(V ') can be mentioned.
β−ジケトンを溶解させる有機溶媒としては、水と分別した相を形成できる有機溶媒が好ましく、具体的な有機溶媒としては、トルエン、ヘキサン、オクタンなどの炭化水素類、ジエチルエーテルなどのエーテル類、酢酸ブチルなどのエステル類、塩化メチレンなどのハロゲン化炭化水素類などが挙げられる。 As the organic solvent for dissolving β-diketone, an organic solvent capable of forming a phase separated from water is preferable. Specific organic solvents include hydrocarbons such as toluene, hexane, and octane, ethers such as diethyl ether, Examples thereof include esters such as butyl acetate and halogenated hydrocarbons such as methylene chloride.
本発明において、カルボン酸銅としては、炭素原子数が１〜６の脂肪族カルボン酸の２価銅塩を使用する。目的物である銅錯体中に残るのは銅だけであることから分子量の大きいものを使用する意味がないだけでなく、水相への溶解特性の上からも好ましくない。炭素原子数が１〜３のモノカルボン酸すなわち、ギ酸、酢酸およびプロピオン酸の２価銅塩が好ましく、特に、酢酸銅は、水に対する溶解特性並びに市場における入手容易性の面から、銅源として好ましい化合物である。 In the present invention, as the carboxylate copper, a divalent copper salt of an aliphatic carboxylic acid having 1 to 6 carbon atoms is used. Since it is only copper that remains in the target copper complex, not only does it not make sense to use one having a large molecular weight, but it is also not preferable from the viewpoint of solubility in an aqueous phase. A monocarboxylic acid having 1 to 3 carbon atoms, that is, a divalent copper salt of formic acid, acetic acid and propionic acid is preferred. In particular, copper acetate is used as a copper source from the viewpoint of solubility in water and availability in the market. Preferred compounds.
本発明のβ−ジケトンとカルボン酸銅との反応においては、例えば酢酸銅の場合を例にとると次式で示される平衡関係が存在する。 In the reaction of the β-diketone and copper carboxylate of the present invention, for example, taking the case of copper acetate as an example, there is an equilibrium relationship represented by the following formula.
反応を完結させるためには、生成するフリーのカルボン酸を反応系から留去する必要がある。反応で生成するフリーのカルボン酸は、有機相−水相の二相のうち、水相に移行し易いため、生成カルボン酸の溶解した水相を有機相から分液することにより、反応で生成するカルボン酸を反応系外に留去することが出来る。水相を留去した後、更に新たにカルボン酸銅水溶液を反応系に添加することにより、上記［化４］で示される反応の平衡を生成系に移衡させ、反応を完結させることができる。すなわち、図１で示されるように反応後、水相を分液し、新たにカルボン酸銅水溶液を有機相に添加する。この反応・分液・カルボン酸銅水溶液添加の操作を繰り返すことにより、反応を完結できる。銅錯体の収率の面からは、この繰り返し操作は多い方が良いが、通常４回反応操作を行うことにより、反応はほぼ完結する。また、過剰にカルボン酸銅を使用しても、水相にほとんど存在することから、水相の分液により、カルボン酸銅を留去できる。
反応後、溶媒の有機溶媒を減圧留去することにより、暗緑色の銅錯体を得、これを更に蒸留精製して高純度の目的のβ−ジケトナト銅錯体が得られる。
以下では、具体例を挙げて、本発明を更に詳しく説明する。
In order to complete the reaction, it is necessary to distill off the produced free carboxylic acid from the reaction system. The free carboxylic acid produced by the reaction is easily transferred to the aqueous phase out of the two phases of the organic phase and the aqueous phase. Therefore, the aqueous phase in which the produced carboxylic acid is dissolved is separated from the organic phase and produced by the reaction. The carboxylic acid to be removed can be distilled out of the reaction system. After distilling off the aqueous phase, by adding a new aqueous solution of copper carboxylate to the reaction system, the equilibrium of the reaction shown in the above [Chemical Formula 4] can be transferred to the production system and the reaction can be completed. . That is, as shown in FIG. 1, after the reaction, the aqueous phase is separated, and a copper carboxylate aqueous solution is newly added to the organic phase. The reaction can be completed by repeating this reaction, liquid separation, and the operation of adding an aqueous solution of copper carboxylate. From the viewpoint of the yield of the copper complex, it is better to perform this repeated operation, but usually the reaction is almost completed by performing the reaction operation four times. Moreover, even if an excessive amount of copper carboxylate is used, since it is almost present in the aqueous phase, the copper carboxylate can be distilled off by liquid separation of the aqueous phase.
After the reaction, the organic solvent as a solvent is distilled off under reduced pressure to obtain a dark green copper complex, which is further purified by distillation to obtain a target β-diketonato copper complex having high purity.
Below, a specific example is given and this invention is demonstrated in more detail.
式（III）で示されるβ−ジケトナト銅錯体 ビス（２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオナト）銅（II）錯体［Ｃｕ(ｓｏｐｄ)２］の合成；
酢酸銅１水和物 １７．９ｇ（８９．７ｍｏｌ）を超純水２８０ｍｌに室温で溶解させ、酢酸銅水溶液を調製した。一方、３００ｍｌのガラス反応容器に２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオン３５．０ｇ（１４３．２ｍｍｏｌ）を７０ｍｌのトルエンに溶解させ、室温下、そのトルエン溶液に先ほど調製した酢酸銅水溶液のうち、１／４にあたる７０ｍｌを添加し、室温下、３０分攪拌し反応させた。その後、水相を分液し、暗緑色のトルエン溶液を得た。続いて、そのトルエン溶液に、残りの酢酸銅水溶液２１０ｍｌのうち、７０ｍｌを添加し、室温下、３０分反応させた後、水相を分液した。この操作を計４回繰り返した後、暗緑色のトルエン溶液が得られた。得られたトルエン溶液を濃縮することにより、暗緑色の粘性液体を得、その暗緑色の粘性液体を１７９℃／６６．７Ｐａ（０．５Ｔｏｒｒ）で蒸留精製することにより、目的の銅錯体、ビス（２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオナト）銅（II）錯体を３７．２ｇ（６７．６ｍｍｏｌ、収率９５％）得た。
Β-diketonato copper complex represented by the formula (III) Synthesis of bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadionato) copper (II) complex [Cu (sopd) 2 ];
Copper acetate monohydrate 17.9 g (89.7 mol) was dissolved in 280 ml of ultrapure water at room temperature to prepare an aqueous solution of copper acetate. Meanwhile, 35.0 g (143.2 mmol) of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadione was dissolved in 70 ml of toluene in a 300 ml glass reaction vessel, and the toluene solution was dissolved at room temperature. Of the copper acetate aqueous solution prepared earlier, 70 ml corresponding to 1/4 was added, and the mixture was stirred at room temperature for 30 minutes to be reacted. Thereafter, the aqueous phase was separated to obtain a dark green toluene solution. Subsequently, 70 ml of the remaining 210 ml of aqueous copper acetate solution was added to the toluene solution and reacted at room temperature for 30 minutes, and then the aqueous phase was separated. After this operation was repeated a total of 4 times, a dark green toluene solution was obtained. The obtained toluene solution is concentrated to obtain a dark green viscous liquid, and the dark green viscous liquid is purified by distillation at 179 ° C./66.7 Pa (0.5 Torr) to obtain the target copper complex, bis 37.2 g (67.6 mmol, 95% yield) of (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadionato) copper (II) complex was obtained.
得られた銅錯体の同定は、ＩＲ、元素分析により行なった。
・ＩＲ（ｃｍ−１）：３４５８（ｂｒ）、２９６３、１５６８、１５１８、１４２２、１２５１、１１９６、１０３５、８８９、８４１
・元素分析：Ｃ２４Ｈ４６Ｏ６Ｓｉ２Ｃｕ
測定値 Ｃ：５３．１％、Ｈ：８．３８％、Ｃｕ：１１．５％
理論値 Ｃ：５２．４％、Ｈ：８．４２％ 、Ｃｕ：１１．５％
融点：６２℃
The obtained copper complex was identified by IR and elemental analysis.
IR (cm −1 ): 3458 (br), 2963, 1568, 1518, 1422, 1251, 1196, 1035, 889, 841
Elemental analysis: C 24 H 46 O 6 Si 2 Cu
Measurement value C: 53.1%, H: 8.38%, Cu: 11.5%
Theoretical value C: 52.4%, H: 8.42%, Cu: 11.5%
Melting point: 62 ° C
この銅錯体のＩＲ分析では、β−ジケトン特有の１６０６ｃｍ−１のピークが消失し、代わりにβ−ジケトナト錯体特有のピーク１５６８ｃｍ−１が得られている。また３４００ｃｍ−１付近に見られるブロードなピークは、銅錯体に配位した結晶水に由来する。なお、蒸留後保存状態が良い場合は、結晶水に由来する３４００ｃｍ−１付近のブロードのピークは見られない。 In the IR analysis of this copper complex, the peak at 1606 cm −1 peculiar to β-diketone disappears, and the peak 1568 cm −1 peculiar to β-diketonato complex is obtained instead. Moreover, the broad peak seen in the vicinity of 3400 cm −1 is derived from crystal water coordinated to the copper complex. In addition, when the preservation | save state is good after distillation, the broad peak near 3400cm < -1 > originating in crystal water is not seen.
次に、実施例１と同一錯体を、水酸化銅及び酢酸銅を使用する不均一反応系で合成した例を夫々比較例１及び比較例２に示す。
比較例１ １００ｍｌのフラスコに水酸化銅４．４３ｇ（４５．４ｍｍｏｌ）を５０ｍｌのトルエンに分散させ、２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオン２２．２ｇ（９０．８ｍｍｏｌ）を入れ反応させた。水酸化銅のトルエンへの溶解度が低いため、固体である水酸化銅が分散して存在する不均一な系での反応である。加熱（１３０℃）下、反応で生成する水をトルエンと共に共沸脱水し、およそ２時間反応後、共沸で生成する水がほぼ出終わったため、反応を終了した。得られた暗緑色の液から未反応の水酸化銅を濾別し、濃縮することによって粘性の暗緑色液体が得られた。その液を１７９℃／６６．７Ｐａ（０．５Ｔｏｒｒ）で蒸留精製することにより、目的の銅錯体、ビス（２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオナト）銅（II）を２０．２ｇ（３６．８ｍｍｏｌ、収率８１％）得た。
Next, examples of synthesizing the same complex as in Example 1 in a heterogeneous reaction system using copper hydroxide and copper acetate are shown in Comparative Example 1 and Comparative Example 2, respectively.
Comparative Example 1 4.43 g (45.4 mmol) of copper hydroxide was dispersed in 50 ml of toluene in a 100 ml flask, and 22.2 g (90 of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadione (90 .8 mmol) was added and reacted. Since the solubility of copper hydroxide in toluene is low, the reaction is in a heterogeneous system in which solid copper hydroxide is present in a dispersed state. Under heating (130 ° C.), the water produced by the reaction was azeotropically dehydrated with toluene, and after the reaction for about 2 hours, the water produced by the azeotrope was almost finished, so the reaction was terminated. Unreacted copper hydroxide was filtered off from the obtained dark green liquid and concentrated to obtain a viscous dark green liquid. The solution was purified by distillation at 179 ° C./66.7 Pa (0.5 Torr) to obtain the target copper complex, bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadionato) copper ( II) was obtained 20.2 g (36.8 mmol, 81% yield).
比較例２ １００ｍｌのフラスコに酢酸銅一水和物９．２２ｇ（４６．２ｍｍｏｌ）をＴＨＦ５０ｍｌに分散させ、２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオン２２．６ｇ（９２．３ｍｍｏｌ）を入れ、室温で２時間攪拌した。得られた暗青色の液から未反応である固体の酢酸銅をろ過後、ＴＨＦ溶媒を留去濃縮することにより、粘性の暗緑色液体が得られた。その液を１７９℃／６６．７Ｐａ（０．５Ｔｏｒｒ）で蒸留精製することにより、目的の銅錯体、ビス（２，６−ジメチル−２−（トリメチルシリロキシ）−３，５−ヘプタジオナト）銅（II）を２１．１ｇ（３８．３ｍｍｏｌ、収率８３％）得た。 Comparative Example 2 In a 100 ml flask, 9.22 g (46.2 mmol) of copper acetate monohydrate was dispersed in 50 ml of THF, and 22.6 g of 2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadione ( 92.3 mmol) was added and stirred at room temperature for 2 hours. After filtering unreacted solid copper acetate from the obtained dark blue liquid, the THF solvent was distilled off and concentrated to obtain a viscous dark green liquid. The solution was purified by distillation at 179 ° C./66.7 Pa (0.5 Torr) to obtain the target copper complex, bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptadionato) copper ( II) was obtained 21.1 g (38.3 mmol, 83% yield).
比較例１では、平衡反応を生成系へ移衡させる操作を行ったが、ジケトンと銅塩との不均一反応系のため、反応が遅く、反応収率が低い。また比較例２でも、ジケトンと銅塩との不均一反応系であるのに加え、平衡反応を生成系へ移衡させることなしに反応させるため、反応収率が低くなる。また、反応後、固体である未反応の銅塩を反応液から濾別する濾過操作が必要であり、大量生産を考慮した工業的製造法として、操作的に問題である。 In Comparative Example 1, an operation for transferring the equilibrium reaction to the production system was performed. However, because of the heterogeneous reaction system of diketone and copper salt, the reaction is slow and the reaction yield is low. Also in Comparative Example 2, in addition to being a heterogeneous reaction system of a diketone and a copper salt, the reaction yield is lowered because the reaction is carried out without transferring the equilibrium reaction to the production system. In addition, after the reaction, a filtration operation is required to separate the unreacted copper salt that is a solid from the reaction solution, which is an operational problem as an industrial production method considering mass production.
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