JPH0278663A - 26-ethylidenenitrilophenylpyridine, production thereof and metal salt complex - Google Patents
26-ethylidenenitrilophenylpyridine, production thereof and metal salt complexInfo
- Publication number
- JPH0278663A JPH0278663A JP63228804A JP22880488A JPH0278663A JP H0278663 A JPH0278663 A JP H0278663A JP 63228804 A JP63228804 A JP 63228804A JP 22880488 A JP22880488 A JP 22880488A JP H0278663 A JPH0278663 A JP H0278663A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- metal salt
- ethylidenenitrilophenylpyridine
- complex
- diacetylpyridine
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 150000003839 salts Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229930003836 cresol Natural products 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract description 6
- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 239000012046 mixed solvent Substances 0.000 abstract description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000005408 paramagnetism Effects 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- -1 hydrazone compound Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical class [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 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 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、２，６−ニチリデンニトリロフエニルピリジ
ン、その製造法ならびに金属塩錯体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 2,6-nitrydenitrilophenylpyridine, a method for producing the same, and a metal salt complex.
更に詳しくは、磁気材料、触媒材料などとして有効な、
高スピン錯体を形成し得る２、６−ニチリデンニトリロ
フエニルピリジン、その製造法ならびに金属塩錯体に関
する。More specifically, effective as magnetic materials, catalytic materials, etc.
The present invention relates to 2,6-nitrydenitrilophenylpyridine capable of forming a high spin complex, a method for producing the same, and a metal salt complex.
〔従来の技術〕および〔発明の課題〕
で表わされる２、６−ジアセチルピリジンビスヒドラゾ
ン化合物およびその金属塩錯体が、工。。ｒｇａｎｉｃ
Ｃｈｅｍｉｓｔｒｙ第６巻第８号第１５７０頁（１９６
７）に記載されている。[Prior Art] and [Problems of the Invention] A 2,6-diacetylpyridine bishydrazone compound and a metal salt complex thereof represented by the following are disclosed. . rganic
Chemistry Vol. 6 No. 8 No. 1570 (196
7).
本発明は、上記−船人［ｍｌで表わされるヒドラゾン化
合物ではなく、Ｒがフェニル基である新規な２，６−ニ
チリデンニトリロフエニルピリジンおよびその金属塩錯
体を提供することを目的としている。The object of the present invention is to provide a novel 2,6-nitrydenitrilophenylpyridine and its metal salt complex, in which R is a phenyl group, rather than the hydrazone compound represented by the above-mentioned -Funen [ml].
本発明に係る２、６−ニチリデンニトリロフエニルピリ
ジンは、次の一般式［１１で表わされる。2,6-Nycylidenenitrilophenylpyridine according to the present invention is represented by the following general formula [11].
かかる２、６−ニチリデンニトリロフエニルビリジンは
、２，６−ジアセチルピリジンおよびアニリンをクレゾ
ール触媒の存在下で反応させることにより得られる。Such 2,6-nitrylidenetrilophenylpyridine can be obtained by reacting 2,6-diacetylpyridine and aniline in the presence of a cresol catalyst.
アセチルピリジンとアニリン（これは低級アルキル基な
どの置換基を有していてもよい）との反応は、アセチル
ピリジン１モルに対してアニリンを２モルまたはそれよ
り若干量多く用い、クロロホルム、トリクロロエタン、
四塩化炭素などの少くとも一種のハロゲン化炭化水素溶
媒中で加熱還元して縮合反応させ、脱水された水はモレ
キュラーシーブや脱水トラップで捕集し、反応を進行さ
せるようにする。The reaction between acetylpyridine and aniline (which may have a substituent such as a lower alkyl group) uses 2 moles or slightly more aniline per mole of acetylpyridine, and chloroform, trichloroethane,
The condensation reaction is caused by thermal reduction in at least one type of halogenated hydrocarbon solvent such as carbon tetrachloride, and the dehydrated water is collected with a molecular sieve or dehydration trap to allow the reaction to proceed.
この際の縮合反応触媒として、０−ｌｍ−またはＰ−ク
レゾール、好ましくはｍ−クレゾールが、２，６−ジア
セチルピリジン１モルに対し約２〜５モルで程度用いら
れ、この触媒を用いないと目的物が得られない。As a condensation reaction catalyst in this case, 0-lm- or P-cresol, preferably m-cresol, is used in an amount of about 2 to 5 mol per 1 mol of 2,6-diacetylpyridine. I can't get what I want.
反応終了後、反応混合物を口過し、口演から溶媒を減圧
下で留去し、残渣をクロロホルム／メタノール混合溶媒
で再結晶することにより、目的物たる２，６−ニチリデ
ンニトリロフエニルピリジンを得ることができる。After the reaction is completed, the reaction mixture is passed through the mouth, the solvent is distilled off under reduced pressure, and the residue is recrystallized with a chloroform/methanol mixed solvent to obtain the target product, 2,6-nitrydenitrilophenylpyridine. Obtainable.
この２，６−ニチリデンニトリロフエニルピリジンは、
これをメタノール、エタノール、水などの金属塩可溶性
溶媒に溶解させ、その溶液中に鉄、銅。This 2,6-nitrydenitrilophenylpyridine is
This is dissolved in a metal salt-soluble solvent such as methanol, ethanol, or water, and iron and copper are dissolved in the solution.
クロム、ニッケル、マンガン、亜鉛などの２〜３価金属
の塩１例えば硫酸塩、硝酸塩、酢酸塩、過塩素酸塩、ハ
ロゲン化物などを添加し、室温条件下、窒素ガス雰囲気
中で攪拌することにより金属錯体化される。それの精製
は１反応混合物を口過し、口演から溶媒を減圧下で留去
し、残渣をエタノール／ｎ−ヘキサンで再沈させること
により行われる。Salts of di- or trivalent metals such as chromium, nickel, manganese, zinc, etc. 1 Adding sulfates, nitrates, acetates, perchlorates, halides, etc., and stirring under room temperature conditions in a nitrogen gas atmosphere. is converted into a metal complex by Its purification is carried out by passing the reaction mixture through the mouth, distilling off the solvent from the mouth under reduced pressure, and reprecipitating the residue with ethanol/n-hexane.
本発明により、新規な２，６−ニチリデンニトリロフエ
ニルビリジンが提供され、次の一般式［１１］で表わさ
れ、金属錯体を形成させる。この金属錯体は、常磁性を
有する高スピン錯体であるため、、触媒材料、磁気材料
などとして有効に利用される。According to the present invention, a novel 2,6-nitrydenitrilophenylpyridine is provided, which is represented by the following general formula [11], and forms a metal complex. Since this metal complex is a high-spin complex with paramagnetic properties, it is effectively used as a catalyst material, a magnetic material, and the like.
（以下余白） 〔実施例〕 次に、実施例について本発明を説明する。(Margin below) 〔Example〕 Next, the present invention will be explained with reference to examples.
実施例１
２．６−ジアセチルピリジン１２．６ｇ（７，７２ｘ
１０−” モル）、アニリン１４．３６ｇ（１５，４Ｘ
１０−”モル）および難−クレゾール１．０ｇをクロ
ロホルム／トリクロロエタン（容積比２／ｌ）混合溶媒
６０ｍ １１に溶がし、８時間還流した。その際１反応
系から生成する水をモレキュラーシーブで除去しながら
１反応を行なった。Example 1 12.6 g of 2.6-diacetylpyridine (7,72x
10-” mol), 14.36 g of aniline (15.4×
10-" mol) and 1.0 g of difficult-cresol were dissolved in 60 ml of a mixed solvent of chloroform/trichloroethane (volume ratio 2/l) and refluxed for 8 hours. At this time, the water produced from the reaction system 1 was purified using a molecular sieve. One reaction was carried out with removal.
反応終了後、反応混合物を口過し、口演から溶媒を減圧
下で留去した後、残渣をクロロホルム／メタノール（容
積比１７５〜１０）混合溶媒で２回再結晶した。前記式
［１］で表わされる２、６−エチリデンニトリロフェニ
ルピリジン８．５ｇ（収率３５％）が得られた。After the reaction was completed, the reaction mixture was passed through the mouth, and the solvent was distilled off from the mouth under reduced pressure, and the residue was recrystallized twice with a mixed solvent of chloroform/methanol (volume ratio 175-10). 8.5 g (yield: 35%) of 2,6-ethylidenenitrilophenylpyridine represented by the above formula [1] was obtained.
その赤外線吸収スペクトルは第１図に示される。Its infrared absorption spectrum is shown in FIG.
このＥＳＲチャートから、この金属塩錯体は常磁性を有
することが分る。また、ＶＳＭ （振動試料型磁力計）
より、χｇ（ダラム磁化率）＝５．６６ｃｍ／ｇの値が
得られた。なお、この化合物は吸湿性物質のため。This ESR chart shows that this metal salt complex has paramagnetism. Also, VSM (vibrating sample magnetometer)
From this, a value of χg (Durham magnetic susceptibility) = 5.66 cm/g was obtained. Please note that this compound is a hygroscopic substance.
融点の測定ができない。Unable to measure melting point.
比較例
実施例１の反応を、ｍ−クレゾールを用いずにクロロホ
ルム１４０ｍ Ｑ中、で行なうと、再結晶により４．０
ｇの固体が得られたが、第３図に示される赤外線吸収ス
ペクトルでのピークＡ（１６９９ｃｍ−’、 Ｃ＝０）
およびピークＢ（１６３７ｃｍ−１，Ｃ＝Ｎ）の存在な
らびにＮＭＲの結果から、−ＣＯＣＨ，／−ＣＮとが１
＝１のモル比で存在する反応中間体の生成が確認される
のみであった。Comparative Example When the reaction of Example 1 was carried out in 140 mQ of chloroform without using m-cresol, 4.0% was obtained by recrystallization.
g of solid was obtained, but peak A (1699 cm-', C=0) in the infrared absorption spectrum shown in Fig. 3 was obtained.
From the presence of peak B (1637 cm-1, C=N) and the NMR results, it is clear that -COCH,/-CN is 1
Only the formation of a reaction intermediate present at a molar ratio of =1 was confirmed.
実施例２
実施例１で得られた２、６−ニチリデンニトリロフエニ
ルピリジン３．１３ｇ（１，ＯＸ １Ｇ−”モル）をエ
タノール５０ｍ Ｑに溶かし、これに水５０ｍ ｍに溶
かしたＦｅ５Ｏ１・７Ｈ２０１，３９ｇ（５０ｘｔＯ−
”モル）を室温条件下、窒素ガス雰囲気下で加えた。直
ちに濃紫色の錯体が生成するが、そのまま１時間攪拌を
継続した。反応混合物を口過し、０液から減圧下に３５
℃以下で溶媒を留去した後再びエタノールに溶かし、ｎ
−ヘキサン中に再沈殿させた。デカンテーション法によ
り。Example 2 3.13 g (1,0X 1 G-" mole) of 2,6-nitrydenitrilophenylpyridine obtained in Example 1 was dissolved in 50 m Q of ethanol, and Fe5O1.7H201 was dissolved in 50 m m of water. , 39g (50xtO-
1 mol) was added under nitrogen gas atmosphere at room temperature. A deep purple complex was immediately formed, but stirring was continued for 1 hour.
After distilling off the solvent at a temperature below ℃, dissolve it again in ethanol, and
-Re-precipitated in hexane. By decantation method.
ｎ−ヘキサンで４回洗浄した後減圧乾燥し、錯体３．３
ｇ（収率８５％）を得た。この硫酸第１鉄錯体の赤外線
吸収スペクトルは、第２図に示される。また、 ＥＳＲ
（電子スピン共鳴）チャートは、第４図に示される。After washing with n-hexane four times and drying under reduced pressure, complex 3.3
g (yield 85%) was obtained. The infrared absorption spectrum of this ferrous sulfate complex is shown in FIG. Also, ESR
(Electron spin resonance) chart is shown in FIG.
実施例３〜５
実施例２において、 ＦｅＳＯ４・７Ｈ２０の代りに、
それぞれ同モル量のＣｏＳＯ４・７Ｈ２０、Ｃｕ５Ｏ，
・５Ｈ，ＯまたはＦｅＣＱ 、・４Ｈ２０を用いると、
対応する金属塩錯体が得られた。Examples 3 to 5 In Example 2, instead of FeSO4.7H20,
Same molar amount of CoSO4・7H20, Cu5O,
・When using 5H,O or FeCQ, ・4H20,
The corresponding metal salt complex was obtained.
第１〜３図は、実施例１〜２および比較例で得られた反
応生成物の赤外線吸収スペクトルである。
また、第４図は、実施例２の反応生成物についてのＥＳ
Ｒチャートである。
手続補正書（１劃
平成元年１月３１日1 to 3 are infrared absorption spectra of the reaction products obtained in Examples 1 to 2 and Comparative Example. Moreover, FIG. 4 shows the ES for the reaction product of Example 2.
This is an R chart. Procedural Amendment (Part 1, January 31, 1989)
Claims (1)
ジン。 ２、２，６−ジアセチルピリジンおよびアニリンをクレ
ゾール触媒の存在下で縮合反応させることを特徴とする
式 ▲数式、化学式、表等があります▼［ I ］ で表わされる２，６−エチリデンニトリロフェニルピリ
ジンの製造法。 ３、式 ▲数式、化学式、表等があります▼［ I ］ で表わされる２，６−エチリデンニトリロフェニルピリ
ジンの金属塩錯体。[Claims] 1. 2,6-ethylidenenitrilophenylpyridine represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I]. A formula characterized by the condensation reaction of 2,2,6-diacetylpyridine and aniline in the presence of a cresol catalyst ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2,6-ethylidenenitrilophenylpyridine represented by [I] manufacturing method. 3. Metal salt complex of 2,6-ethylidenenitrilophenylpyridine represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228804A JPH0278663A (en) | 1988-09-14 | 1988-09-14 | 26-ethylidenenitrilophenylpyridine, production thereof and metal salt complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228804A JPH0278663A (en) | 1988-09-14 | 1988-09-14 | 26-ethylidenenitrilophenylpyridine, production thereof and metal salt complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0278663A true JPH0278663A (en) | 1990-03-19 |
Family
ID=16882116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63228804A Pending JPH0278663A (en) | 1988-09-14 | 1988-09-14 | 26-ethylidenenitrilophenylpyridine, production thereof and metal salt complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0278663A (en) |
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| WO1998027124A1 (en) * | 1996-12-17 | 1998-06-25 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis(imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
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| US6127529A (en) * | 1988-06-29 | 2000-10-03 | Wallac Oy | Metal-chelating 2,6-disubstituted pyridine compounds and their use |
| WO2001023396A1 (en) * | 1999-09-29 | 2001-04-05 | Bp Chemicals Limited | Polymerisation catalyst |
| US6214761B1 (en) | 1996-12-17 | 2001-04-10 | E. I. Du Pont De Nemours And Company | Iron catalyst for the polymerization of olefins |
| US6265505B1 (en) | 1999-11-18 | 2001-07-24 | Univation Technologies, Llc | Catalyst system and its use in a polymerization process |
| US6271325B1 (en) | 1999-05-17 | 2001-08-07 | Univation Technologies, Llc | Method of polymerization |
| US6271323B1 (en) | 1999-10-28 | 2001-08-07 | Univation Technologies, Llc | Mixed catalyst compounds, catalyst systems and their use in a polymerization process |
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| US6417305B2 (en) | 1996-12-17 | 2002-07-09 | E. I. Du Pont De Nemours And Company | Oligomerization of ethylene |
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| US6432862B1 (en) | 1996-12-17 | 2002-08-13 | E. I. Du Pont De Nemours And Company | Cobalt catalysts for the polymerization of olefins |
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| US6686306B2 (en) | 2001-04-30 | 2004-02-03 | W.R. Grace & Co.- Conn. | Supported dual transition metal catalyst systems |
| US6734131B2 (en) | 2001-04-30 | 2004-05-11 | W. R. Grace & Co.-Conn. | Heterogeneous chromium catalysts and processes of polymerization of olefins using same |
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