JPH0314525A - Production of diacenaphthyls - Google Patents
Production of diacenaphthylsInfo
- Publication number
- JPH0314525A JPH0314525A JP1146789A JP14678989A JPH0314525A JP H0314525 A JPH0314525 A JP H0314525A JP 1146789 A JP1146789 A JP 1146789A JP 14678989 A JP14678989 A JP 14678989A JP H0314525 A JPH0314525 A JP H0314525A
- Authority
- JP
- Japan
- Prior art keywords
- acenaphthene
- nickel
- diacenaphthyls
- halide
- anhydrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- XIDFXORSALFWOP-UHFFFAOYSA-N 5-chloro-1,2-dihydroacenaphthylene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3Cl XIDFXORSALFWOP-UHFFFAOYSA-N 0.000 claims abstract description 4
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 20
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 13
- 150000001239 acenaphthenes Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- DRZNOPRRQNUPSF-UHFFFAOYSA-N 1-bromo-1,2-dihydroacenaphthylene Chemical compound C1=CC(C(Br)C2)=C3C2=CC=CC3=C1 DRZNOPRRQNUPSF-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- -1 (substituted) acenaphthene halide Chemical class 0.000 abstract description 7
- QALKJGMGKYKMKE-UHFFFAOYSA-N 5-bromo-1,2-dihydroacenaphthylene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3Br QALKJGMGKYKMKE-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 4
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000004642 Polyimide Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 229920001721 polyimide Polymers 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- ANIXIIYQBGBGRI-UHFFFAOYSA-N 1-chloro-1,2-dihydroacenaphthylene Chemical compound C1=CC(C(Cl)C2)=C3C2=CC=CC3=C1 ANIXIIYQBGBGRI-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical group [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アセナフテン又は置換アセナフテンのハロゲ
ン化物をカップリング反応させてジアセナフチル類を製
造する方広に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a process for producing diacenaphthyls by coupling acenaphthene or a halide of substituted acenaphthene.
ジアセナフチル類は、公知の方法、例えば重クロム酸ナ
トリウム等で酸化する方法により容易に酸化され、酸無
水物を与える。そして、この酸無水物は、ポリイミド製
造用モノマーや顔料の原料として利用できる。Diacenaphthyls are easily oxidized by known methods, such as oxidation with sodium dichromate, to give acid anhydrides. This acid anhydride can be used as a raw material for monomers and pigments for producing polyimide.
ところで、アリールーアリールのカップリング反応は、
有機合成において極めて有用な反応であり、通常、金属
触媒が使用される。そして、触媒として銅を使用したい
わゆるウルマン（Ｕｌｌｍａｎｎ）反応がケミカルレビ
ュー（Ｃｈｅｍ． Ｒｅｖ．）， ３８， １３９（１
９４６）及び同６４， ６１３（１９６４）に記載され
ている。By the way, the ary-aryl coupling reaction is
This is an extremely useful reaction in organic synthesis, and metal catalysts are usually used. The so-called Ullmann reaction using copper as a catalyst was published in Chem. Rev., 38, 139 (1).
946) and 64, 613 (1964).
また、触媒としてパラジウム錯体を使用した例がジャー
ナル．オブ．ザ．ケミカル．ソサエティー（Ｊ． Ｃｈ
ｅｍ． Ｓｏｃ．）パーキンＩ （Ｐｅｒｋｉｎ Ｉ）
， １２１（１９７５）に記載されている。また、触媒
としてニッケル錯体を使用した例がジャーナル．オブ．
ジ，アメリカン．ケミカル．ソサエティー（Ｊ． Ａｍ
． Ｃｈｅｍ． Ｓｏｃ．）， ９３． ５９０８（１
９７１）、特開昭５６−４０， ６１５号公報及びジャ
ーナル．オブ．オルガニック．ケミストリイ−（Ｊ．
Ｏｒｇ． Ｃｈｅｍ．）， ５１． ２６２７（１９
８６）に記載されている。 そして、上記特開昭５６−
４０，６１５号公報においては、クロロベンゼン誘導体
のカップリング反応において、錯体の形成に必要なニッ
ケル化合物、還元性金属（亜鉛、マンガン等）、配位子
及び助触媒である無機塩の種類や添加量が反応に及ぼす
影響を詳細に検討している。Journal also provides an example of using a palladium complex as a catalyst. of. The. chemical. Society (J. Ch.
em. Soc. ) Perkin I
, 121 (1975). Journal also provides an example of using a nickel complex as a catalyst. of.
The American. chemical. Society (J. Am
．． Chem. Soc. ), 93. 5908 (1
971), JP-A-56-40, 615 and Journal. of. Organic. Chemistry (J.
Org. Chem. ), 51. 2627 (19
86). And, the above-mentioned Unexamined Patent Publication No. 56-
Publication No. 40,615 discloses the types and amounts of nickel compounds, reducing metals (zinc, manganese, etc.), ligands, and inorganic salts as co-catalysts necessary for complex formation in the coupling reaction of chlorobenzene derivatives. The effect of this on the reaction is examined in detail.
しかしながら、パラジウムやニッケルの錯体触媒を使用
する上記２つの方法は、そのいずれもベンゼン誘導体に
ついてのみ検討を行っているにすぎず、アセナフテン化
合物のカップリングについては具体的に教えるものがな
い。However, both of the above two methods using complex catalysts of palladium or nickel only examine benzene derivatives, and do not specifically teach coupling of acenaphthene compounds.
そして、ジアセナフチル類の製造方法については、カナ
ディアン．ジャーナル．オブ．ケミカル（Ｃａｎ． Ｊ
． Ｃｈｅｍ．） ５１． １８３３（１９７３）にお
いてグリニャール（Ｇｒｉｇｎａｒｄ）試薬を使用した
アセナフテンのカップリング反応が報告されているにす
ぎない。For the production method of diacenaphthyls, please refer to Canadian. journal. of. Chemical (Can. J
．． Chem. ) 51. 1833 (1973) only reported the coupling reaction of acenaphthene using a Grignard reagent.
しかしながら、この方法は、収率が４９％程度であって
工業的に実施するには低すぎるという問題があった。However, this method had a problem in that the yield was about 49%, which was too low to be implemented industrially.
本発明の目的は、アセナフテン類のカップリング反応生
成物であるジアセナフチル類を高収率で製造し得る方法
を提供することにある。An object of the present invention is to provide a method for producing diacenaphthyls, which are coupling reaction products of acenaphthenes, in high yield.
即ち、本発明は、アセナフテン又は置換アセナフテンの
ハロゲン化物を、還元性金属、無水ニッケル化合物及び
トリアリールホスフィンの存在下に非プロトン性溶媒中
で反応さ、下記一般式（但し、式中Ｒはアルキル基又は
アルコキシ基を示す）で表されるジアセナフチル類を製
造する方法である。That is, in the present invention, a halide of acenaphthene or a substituted acenaphthene is reacted in an aprotic solvent in the presence of a reducing metal, an anhydrous nickel compound, and a triarylphosphine, and is prepared by the following general formula (wherein R is alkyl This is a method for producing diacenaphthyls represented by the following formula (representing a group or an alkoxy group).
本発明で使用するアセナフテン又は置換アセナフテンの
ハロゲン化物としては、モノクロル化物やモノブロム化
物が好ましく、より好ましくは、５−クロルアセナフテ
ン及び５−ブロムアセナフテンである。また、置換アセ
ナフテンとしては、上記置換基Ｒがアルキル基又はアル
コキシ基であり、好ましくは低級アルキル基又は低級ア
ルコキシ基であり、より好ましくはメチル基やメトキシ
基である。The halogenated acenaphthene or substituted acenaphthene used in the present invention is preferably a monochloride or a monobrominated product, and more preferably 5-chloroacenaphthene and 5-bromoacenaphthene. Further, in the substituted acenaphthene, the substituent R is an alkyl group or an alkoxy group, preferably a lower alkyl group or a lower alkoxy group, and more preferably a methyl group or a methoxy group.
また、本発明で使用する還元性金属としては、好ましく
は金属マンガン、金属亜鉛等を挙げることができ、より
好ましくは金属亜鉛である。そして、これらの還元性金
属を使用する場合には、その使用に先駆けて希塩酸水溶
液等の酸水溶液で洗浄し、充分に乾燥させる前処理を行
うのがよい。Preferably, the reducing metal used in the present invention includes metal manganese, metal zinc, and the like, and metal zinc is more preferable. When these reducing metals are used, it is preferable to perform pretreatment by washing them with an acid aqueous solution such as a dilute hydrochloric acid aqueous solution and drying them thoroughly before use.
反応溶媒として使用する非プロトン性溶媒としては、ジ
メチルホルムアミド、ジメチルアセトアミド、ジメチル
スルホキシド、スルホラン等があり、好ましくはジメチ
ルホルムアミドやジメチルアセトアミドである。これら
の非プロトン性溶媒については、その使用に先駆けて脱
水処理し、無水溶媒として使用するのが好ましい。Examples of the aprotic solvent used as a reaction solvent include dimethylformamide, dimethylacetamide, dimethylsulfoxide, and sulfolane, with dimethylformamide and dimethylacetamide being preferred. These aprotic solvents are preferably dehydrated prior to use and used as anhydrous solvents.
さらに、本発明方法で使用する触媒混合物を調製するた
めのニッケル化合物としては、例えば塩化ニッケル、臭
化ニッケル、沃化ニッケル等のハロゲン化ニッケルや、
硫酸ニッケル、燐酸ニッケル、炭酸ニッケル、蓚酸ニッ
ケルや酢酸ニッケル等の炭素数１−１８の有機酸ニッケ
ル、ニッケルアセチルアセトンやジクロロービス（トリ
フエニルホスフィン）ニッケル（ＩＩ）等のようなニッ
ケル有機錯体、ビス（１，５−シクロオクタジェン）ニ
ッケルやテトラキス（トリフエニルホスフィン）ニッケ
ル等のようなニッケル（０）化合物等を挙げることがで
き、これらは無水である必要がある。そして、これらの
うち好ましいものは、無水塩化ニッケルである。また、
この触媒混合物を調製する際にその配位子として使用さ
れるトリアリールホスフィンとしては、例えばトリフエ
ニルホスフィン、炭素数８個までのアルキル基やアルコ
キシ基を有する置換トリフエニルホスフィン、トリナフ
チルホスフィン、炭素数８個までのアルキル基やアルコ
キシ基を有する置換トリナフチルホスフィン等を挙げる
ことができ、好ましくはトリフェニルホスフィンである
。Furthermore, nickel compounds for preparing the catalyst mixture used in the method of the invention include, for example, nickel halides such as nickel chloride, nickel bromide, nickel iodide,
Nickel sulfate, nickel phosphate, nickel carbonate, nickel carbon atoms such as nickel oxalate and nickel acetate, nickel organic complexes such as nickel acetylacetone and dichlorobis(triphenylphosphine)nickel(II), bis(1 , 5-cyclooctadiene) nickel, tetrakis(triphenylphosphine) nickel, etc., and these need to be anhydrous. Among these, preferred is anhydrous nickel chloride. Also,
The triarylphosphines used as ligands in the preparation of this catalyst mixture include, for example, triphenylphosphine, substituted triphenylphosphine having an alkyl group or alkoxy group having up to 8 carbon atoms, trinaphthylphosphine, carbon Examples include substituted trinaphthylphosphine having up to eight alkyl groups or alkoxy groups, and triphenylphosphine is preferred.
本発明方法において、カップリング反応は、特開昭５６
−４０， ６１５号公報に記載された方法に準じて行う
ことができる。例えば、以下のような方法で行われる。In the method of the present invention, the coupling reaction is
It can be carried out according to the method described in JP-A-40,615. For example, this is done in the following way.
先ず、無水ニッケル化合物、配位子としてのトリアリー
ルホスフィン及び還元性金属を好ましくは不活性ガス雰
囲気下に非プロトン性溶媒中で混合し、６０〜９０℃の
温度に加熱し、触媒混合物を調製する。First, an anhydrous nickel compound, a triarylphosphine as a ligand, and a reducing metal are mixed in an aprotic solvent, preferably under an inert gas atmosphere, and heated to a temperature of 60 to 90 °C to prepare a catalyst mixture. do.
次に、このようにして調製した触媒混合物を６０〜９０
°Ｃの温度に加熱しながら、上記アセナフテン類（アセ
ナフテン又は置換アセナフテン）のハロゲン化物を攪拌
下に好ましくはゆっくりと滴下し、通常５〜２０時間接
触させて反応させる。Next, the catalyst mixture thus prepared was heated to 60-90%
While heating to a temperature of .degree. C., the halide of the acenaphthene (acenaphthene or substituted acenaphthene) is preferably slowly added dropwise with stirring, and the mixture is allowed to react by contacting the mixture for usually 5 to 20 hours.
この時、ニッケルとアセナフテン類のハロゲン化物との
モル比は０．ＯＩ〜０．５の範囲であり、配位子である
トリアリールホスフィンとニッケルとのモル比は１−１
０の．範囲であり、また、還元性金属とアセナフテン類
のハロゲン化物とのモル比は少なくとも０．５である。At this time, the molar ratio of nickel to acenaphthene halides is 0. The OI is in the range of ~0.5, and the molar ratio of the ligand triarylphosphine to nickel is 1-1.
0. and the molar ratio of reducing metal to acenaphthene halide is at least 0.5.
本発明の反応は、必ずしも不活性ガス雰囲気下で行う必
要はないが、不活性ガス雰囲気下で行うことがより好ま
しい。Although the reaction of the present invention does not necessarily have to be carried out under an inert gas atmosphere, it is more preferable to carry out the reaction under an inert gas atmosphere.
以下、実施例に基づいて、本発明方法を具体的に説明す
る。Hereinafter, the method of the present invention will be specifically explained based on Examples.
実施例ｌ
５ｗｔＸ−塩化水素水溶液に浸漬して処理した後、水、
エタノール及びエーテルで洗浄し、減圧下に充分に乾燥
して得られた亜鉛末ｌ１．４重量部、無水塩化ニッケル
０．８重量部及びトリフェニルホスフィン１２．２重量
部を反応容器に仕込み、次いで脱気した後、反応容器内
を窒素ガスで置換した。次に、この反応容器内に無水ジ
メチルホルムアミド（ＤＭＦ）３０重量部を添加し、８
０°Ｃに加熱しながら攪拌し、赤褐色のニッケル（０）
錯体からなる触媒混合物を調製した。 このようにして
調製した触媒混合物を引続き８０℃に加熱しながら、５
−ブロムアセナフテン２７．０重量部の無水ＤＭＦ ３
０重量部溶液を攪拌下にゆっくりと滴下し、滴下終了
後、更に８時間加熱攪拌下に反応を継続した。Example 1 After treatment by immersion in 5wtX-hydrogen chloride aqueous solution, water,
1.4 parts by weight of zinc powder obtained by washing with ethanol and ether and thoroughly drying under reduced pressure, 0.8 parts by weight of anhydrous nickel chloride, and 12.2 parts by weight of triphenylphosphine were charged into a reaction vessel, and then After degassing, the inside of the reaction vessel was replaced with nitrogen gas. Next, 30 parts by weight of anhydrous dimethylformamide (DMF) was added to the reaction vessel, and 8 parts by weight of anhydrous dimethylformamide (DMF) were added.
Stir while heating to 0 °C, reddish brown nickel (0)
A catalyst mixture consisting of the complex was prepared. The catalyst mixture thus prepared was heated to 80°C for 5
- 27.0 parts by weight of bromoacenaphthene in anhydrous DMF 3
0 parts by weight of the solution was slowly added dropwise while stirring, and after the addition was completed, the reaction was continued for an additional 8 hours while stirring with heating.
また、反応混合物の一部を採取し、ガスクロマトグラフ
ィーにより分析した結果、原料の５−ブロムアセナフテ
ンが転化率９１％で５，５゜−ジアセナフチルに転化し
ていることが確認された。Further, a portion of the reaction mixture was sampled and analyzed by gas chromatography. As a result, it was confirmed that the raw material, 5-bromoacenaphthene, had been converted to 5,5°-diacenaphthyl at a conversion rate of 91%.
実施例２
５−ブロムアセナフテンに代えて５−クロロアセナフテ
ンを使用した以外は、上記実施例１と同様にして反応を
行い、５，５゜−ジアセナフチルを製造した。また、ガ
スクロマトグラフィーによる分析の結果、この時の５−
クロロアセナフテンの転化率が８５％であることを確認
した。Example 2 A reaction was carried out in the same manner as in Example 1 above, except that 5-chloroacenaphthene was used in place of 5-bromoacenaphthene, to produce 5,5°-diacenaphthyl. In addition, as a result of analysis by gas chromatography, the 5-
It was confirmed that the conversion rate of chloroacenaphthene was 85%.
本発明の製造方法によれば、ハロゲン化アセナフテン類
からジアセナフチル類をほぼ定量的に得ることができる
。According to the production method of the present invention, diacenaphthyls can be obtained almost quantitatively from halogenated acenaphthenes.
Claims (3)
物を、還元性金属、無水ニッケル化合物及びトリアリー
ルホスフィンの存在下に非プロトン性溶媒中で反応させ
ることを特徴とする下記一般式 ▲数式、化学式、表等があります▼ （但し、式中Ｒはアルキル基又はアルコキシ基を示す）
で表されるジアセナフチル類の製造方法。(1) The following general formula is characterized by reacting acenaphthene or a halide of substituted acenaphthene in an aprotic solvent in the presence of a reducing metal, an anhydrous nickel compound, and triarylphosphine ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R represents an alkyl group or an alkoxy group)
A method for producing diacenaphthyls represented by
の混合物である請求項１記載のジアセナフチル類の製造
方法。(2) The method for producing diacenaphthyls according to claim 1, wherein the reducing metal is zinc, manganese, or a mixture thereof.
−ブロムアセナフテンである請求項１又は２記載のジア
セナフチル類の製造方法。(3) The halide is 5-chloroacenaphthene or 5
-The method for producing diacenaphthyls according to claim 1 or 2, which is bromoacenaphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1146789A JPH0314525A (en) | 1989-06-12 | 1989-06-12 | Production of diacenaphthyls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1146789A JPH0314525A (en) | 1989-06-12 | 1989-06-12 | Production of diacenaphthyls |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0314525A true JPH0314525A (en) | 1991-01-23 |
Family
ID=15415576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1146789A Pending JPH0314525A (en) | 1989-06-12 | 1989-06-12 | Production of diacenaphthyls |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0314525A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016039262A1 (en) * | 2014-09-08 | 2016-03-17 | 昭和電工株式会社 | Method for producing fullerene derivative |
-
1989
- 1989-06-12 JP JP1146789A patent/JPH0314525A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016039262A1 (en) * | 2014-09-08 | 2016-03-17 | 昭和電工株式会社 | Method for producing fullerene derivative |
| CN107074678A (en) * | 2014-09-08 | 2017-08-18 | 昭和电工株式会社 | The manufacture method of fullerene derivate |
| US10526293B2 (en) | 2014-09-08 | 2020-01-07 | Showa Denko K.K. | Method for producing fullerene derivative |
| CN110981679A (en) * | 2014-09-08 | 2020-04-10 | 昭和电工株式会社 | Method for producing halogenated compound and fullerene derivative |
| CN107074678B (en) * | 2014-09-08 | 2020-11-06 | 昭和电工株式会社 | Method for producing fullerene derivative |
| US11136298B2 (en) | 2014-09-08 | 2021-10-05 | Showa Denko K.K. | Method for producing fullerene derivative |
| CN110981679B (en) * | 2014-09-08 | 2023-02-17 | 昭和电工株式会社 | Method for producing halogenated compound and fullerene derivative |
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