WO2010134193A1 - ピリジン化合物の製造方法およびピリジン化合物 - Google Patents
ピリジン化合物の製造方法およびピリジン化合物 Download PDFInfo
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- WO2010134193A1 WO2010134193A1 PCT/JP2009/059406 JP2009059406W WO2010134193A1 WO 2010134193 A1 WO2010134193 A1 WO 2010134193A1 JP 2009059406 W JP2009059406 W JP 2009059406W WO 2010134193 A1 WO2010134193 A1 WO 2010134193A1
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- Prior art keywords
- compound
- pyridine
- aluminum hydride
- pyridine compound
- pyrazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
Definitions
- the present invention relates to a method for producing at least one compound selected from the group consisting of pyridine and derivatives thereof (hereinafter referred to as “pyridine compound”) and a pyridine compound obtained by the method.
- Pyridine compounds having a pyridine ring such as pyridine, picoline, and lutidine are widely used as raw materials for various organic synthetic substances, pharmaceuticals, and agricultural chemicals, or as solvents.
- Various methods for producing a pyridine compound are known, and representative examples include a method for recovering from tar and a synthesis method represented by the titivabine method.
- Examples of such methods include the following: A method of performing distillation after irradiating the pyridine compound with ultraviolet rays (Patent Document 1), A method of treating a pyridine compound with a halogen such as chlorine, bromine, iodine (Patent Document 2), A method of forming a salt with an acid and then treating with activated carbon (Patent Document 3), A method of treating with a halogen-containing sulfur or phosphorus compound (Patent Document 4), A method of treating with isocyanates (Patent Document 5), A method of adding methanol and water for distillation (Patent Document 6), A method of contact treatment with a porous resin (Patent Document 7), A method of treating with an alkaline earth metal oxide or hydroxide (Patent Document 8), A method of treating a solid alkali in the gas phase (Patent Document 9), A method of treating and distilling with permanganate or dichromate (Patent Document 10) and a method of distillation after heating with metal copper
- the colored substance removed by the above method or the causative substance of coloration over time is not accurately identified. It is considered that amines, alcohols and / or aldehydes are contained in the causative substances.
- the produced pyridine compound may contain impurities other than these.
- impurities include two compounds of the benzene ring substituted with nitrogen, such as a compound having a pyrazine ring (pyrazine compound), a compound having a pyrimidine ring (pyrimidine compound), and a compound having a pyridazine ring (pyridazine compound). And a compound having a diazine ring (diazine compound). No effective removal method has been reported for these.
- Impurities composed of such diazine compounds using pyridine as an example. Impurities that are particularly likely to be problematic are pyrazine, pyrimidine, and pyridazine. Table 1 summarizes the normal boiling points and melting points of pyridine, pyrazine, pyrimidine, and pyridazine.
- pyrazine and pyrimidine cannot be easily separated by distillation because they have a standard boiling point close to that of pyridine.
- pyrazine has a standard boiling point very similar to that of pyridine, and it is difficult to completely separate by rectification.
- methylpyrazine, methylpyrimidine, etc. may be contained in pyridine as an impurity, or pyrazine, pyrimidine, etc. may be contained in methylpyridine as an impurity. In this case, separation by distillation is difficult because the standard boiling point is close.
- pyridine and diazine compounds have been well investigated.
- a description of pyridine and pyrazine is as follows. Both NaNH 2 and the like undergo a nucleophilic substitution reaction on carbon to give aminopyridine and aminopyrazine, respectively.
- Alkyl halides undergo an electrophilic reaction on nitrogen to give N-alkylpyridinium and N-alkylpyrazinium, respectively. Oxidized with hydrogen peroxide or the like to become the corresponding N-oxide. With respect to reduction, when completely reduced, it becomes piperidine and piperazine, respectively.
- Non-Patent Documents 2 and 3 There is a report that pyridine reacts with lithium aluminum hydride to give a dihydropyridylaluminum complex.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for efficiently and simply producing a pyridine compound from a crude pyridine compound containing a diazine compound as an impurity, and a pyridine compound produced by the method.
- the inventors applied the purification method for pyridine compounds reported so far to pyridine containing diazine compounds such as pyrazine and pyrimidine as impurities. However, none of them had a purification effect or was very limited.
- the method for producing a pyridine compound according to one embodiment of the present invention includes a reaction step in which a crude pyridine compound is reacted with an aluminum hydride compound, and a distillation step in which a reaction product obtained by the reaction step is distilled. To do.
- the “pyridine compound” refers to a compound having a pyridine ring, that is, at least one compound selected from the group consisting of pyridine derivatives and pyridine.
- This pyridine compound can be obtained by subjecting the crude product (this crude product is also referred to as “crude pyridine compound” in the present invention) to a purification step.
- the pyridine compound according to one embodiment of the present invention contains 99.9% by mass or more of pyridine, the content of the pyrazine compound contained as an impurity is less than 3 mass ppm, and the content of the pyrimidine compound is less than 2 mass ppm. is there.
- the content of pyrazine and pyrimidine can be quantified, for example, by gas chromatography.
- the pyridine according to another embodiment of the present invention includes 99.9% by mass or more of pyridine and has an absorbance per unit length at 320 nm of 0.04 cm ⁇ 1 or less.
- the production method of the present invention can produce a highly pure pyridine compound efficiently and simply. According to this production method, it is possible to obtain a pyridine compound in which the content of the diazine compound as an impurity is very small and the purity of pyridine is particularly high. As shown in Tables 1 and 2, in particular, pyridine compounds, pyrazine compounds, and pyrimidine compounds have close standard boiling points and are often difficult to separate by distillation. Furthermore, pyrazine compounds have a relatively strong UV absorption peak around 320 nm, and if these are included as impurities, the properties of UV absorption are greatly affected. According to the present invention, it is possible to obtain a pyridine compound having extremely low UV absorption derived from such impurities and particularly high purity of pyridine.
- this pyridine compound does not substantially have impurity-derived UV absorption, it can be used without problems for optical applications. In addition, it can be optimally used as a reaction raw material and a solvent, and it is expected that generation of colored substances and substances that cause coloring over time can be suppressed.
- a method for producing a pyridine compound according to an embodiment of the present invention includes a reaction step of reacting a crude pyridine compound with an aluminum hydride compound, and a distillation step of distilling a reaction product obtained by the reaction step.
- the pyridine compound in the present invention means “a compound having a pyridine ring, that is, at least one compound selected from the group consisting of a pyridine derivative and pyridine”.
- pyridine compounds other than pyridine are also referred to as “substituted pyridines”.
- the substituent of the substituted pyridine is not particularly limited. There is no restriction
- the substitution position is not particularly limited as long as it is other than the 1 (N) position. From the viewpoint of increasing the yield and reducing the content of impurities more efficiently, a substituent that does not react with the aluminum hydride compound is preferable.
- an especially preferred example of the substituent is an alkyl group. More preferably, the substituent is an alkyl group having 6 or less carbon atoms.
- alkylpyridines include, for example, 2, 3, and 4-methylpyridine ( ⁇ , ⁇ , and ⁇ -picoline), 2, 3, and 4-ethylpyridine, 2, 3, and 4-n-propylpyridine.
- the “diazine compound” in the present invention is a general term for a pyrazine compound (a compound having a pyrazine ring), a pyrimidine compound (a compound having a pyrimidine ring), and a pyridazine compound (a compound having a pyridazine ring), and has a diazine ring.
- a pyrazine compound a compound having a pyrazine ring
- a pyrimidine compound a compound having a pyrimidine ring
- a pyridazine compound a compound having a pyridazine ring
- the method for preparing the crude pyridine compound, which is the reactant in the above reaction step is not particularly limited, and may be a synthetic product obtained by a method such as the ticibabin method, or a crude product recovered from tar or the like.
- the aluminum hydride compound reacted with the crude pyridine compound in the reaction step is a compound having one or more aluminum-hydride hydrogen bonds (Al—H bonds) in the molecule.
- Al—H bonds aluminum-hydride hydrogen bonds
- it is represented by any one of the following general formulas (1) to (3).
- A is an alkali metal, p is any one of 0, 1, 2, or 3, and R 1 is an alkyl group or an alkoxyalkyl group having one ether group therein) .
- AlHR 2 R 3 (2) (Wherein R 2 and R 3 are each independently hydrogen or an alkyl group).
- AlHR 2 R 3 (NR 4 R 5 R 6 ) n (3) (Wherein R 2 and R 3 are each independently hydrogen or an alkyl group, n is either 1 or 2, and R 4 , R 5 and R 6 are each independently hydrogen, an alkyl group or Any one of the alkenyl groups, and two or all of R 4 , R 5 and R 6 may be linked).
- the aluminum hydride compound represented by the general formula (1) include lithium aluminum hydride LiAlH 4 , sodium aluminum hydride NaAlH 4 , and sodium bis (2-methoxyethoxy) aluminum NaAlH 2 (OCH 2 CH 2 OCH 3 ).
- the aluminum hydride compound represented by the general formula (2) include alane AlH 3 , methylalane CH 3 AlH 2 , dimethylalane (CH 3 ) 2 AlH, and diisobutylaluminum hydride [(CH 3 ) 2. CHCH 2 ] 2 AlH.
- Particularly preferable examples of the aluminum hydride compound represented by the general formula (3) include trimethylamine allane AlH 3 (N (CH 3 ) 3 ), triethylamine allane AlH 3 (N (CH 2 CH 3 ) 3 ), and diethylmethyl.
- N-Methylpyrrolidine Alane N-Methyl Morpho Mention may be made of phosphorus alane and 1-methyl-3-pyrroline alane.
- the aluminum hydride compound may be a pure substance, or a solvent (for example, an aliphatic ether such as diethyl ether, a cyclic ether such as tetrahydrofuran, an aliphatic hydrocarbon such as hexane or heptane, benzene, toluene, etc. May be used in a state dissolved in an aromatic hydrocarbon).
- a solvent for example, an aliphatic ether such as diethyl ether, a cyclic ether such as tetrahydrofuran, an aliphatic hydrocarbon such as hexane or heptane, benzene, toluene, etc. May be used in a state dissolved in an aromatic hydrocarbon).
- reaction conditions for the crude pyridine compound and the aluminum hydride compound are not particularly limited, and can be appropriately selected from various conditions.
- the reaction temperature can also be selected as appropriate.
- About reaction time Preferably it is 1 minute or more.
- the upper limit of the reaction time is not particularly limited as long as it is an environment in which impurities such as moisture are not mixed from the outside.
- the mixing ratio of the crude pyridine compound and the aluminum hydride compound should be determined from the content of impurities including moisture in the crude pyridine compound. Special attention should be paid to the water content, and the added aluminum hydride compound should remain sufficient to remove the remaining impurities after reacting with all the water. In some cases, a pyridine compound dehydrated in advance and an aluminum hydride compound may be reacted.
- a distillation step of distilling the reactant obtained in the reaction step is performed.
- the specific operation is not particularly limited as long as the pyridine compound can be isolated from the reaction product by distillation.
- the reaction solution may be distilled after removing insolubles by filtration. Or you may distill directly from a reaction liquid, without filtering. More preferably, the distillation is not performed once but it is preferable to perform simple distillation first and then perform rectification.
- the distillation may be atmospheric distillation or vacuum distillation.
- GC Gas Chromatography
- ⁇ Detection method FID
- ⁇ Vaporization chamber temperature detector temperature: 150 °C -Sample: Using an autoinjector AOC-20i, inject 2.0 ⁇ L
- -Detection limit The density
- the lithium aluminum hydride used for purification was a reagent manufactured by Kanto Chemical Co., Inc. (Comparative Example 1) To 49.1 g of synthetic pyridine lot 1, 2.0 g of calcium hydride (manufactured by Kanto Chemical Co., Inc.) was added to obtain a slurry. The slurry was stirred for 30 minutes at room temperature and then subjected to simple distillation at normal pressure. Heating was performed in an oil bath and set to 150 ° C. The top temperature was 112 to 116 ° C. A simple distillation yielded 17.2 g (35.0%) fraction. The obtained fraction was subjected to UV measurement. As a result, no improvement was observed in the absorbance at 320 nm.
- Impurity content Pyrazine 17 ppm by mass, and Pyrimidine 12 ppm by mass.
- a slurry was obtained by adding 1.44 g of lithium aluminum hydride to 991.4 g of synthetic pyridine lot 1. After the slurry was refluxed for 30 minutes, simple distillation was performed under the same conditions as in Comparative Example 1. As a result, 77.5 g of the first fraction (distillation rate: 0 to 7.8%), 812.9 g of the main fraction (distillation rate: ⁇ 89.8%), and 66.0 g of the subsequent fraction ( Distillation rate: ⁇ 96.5%). The obtained main fraction (purified pyridine) was subjected to UV measurement. As a result, the 320 nm absorbance of the purified pyridine was greatly reduced to 0.0259. In the GC analysis of this fraction (purified pyridine), no peaks of pyrazine, pyrimidine, and other impurities were observed (Table 4).
- a slurry was obtained by adding 0.15 g of lithium aluminum hydride to 100 g of reagent pyridine. The slurry was refluxed for 30 minutes, and then subjected to simple distillation under the same conditions as in Comparative Example 1, 13.0 g of the initial fraction (distillation rate: 0 to 13.0%), and 68.8 g of the main fraction (distillation). (Distillation rate: ⁇ 81.8%), and 7.8 g of the latter fraction (distillation rate: ⁇ 89.6%).
- the obtained main fraction (purified pyridine) was subjected to UV measurement. As a result, the 320 nm absorbance decreased to 0.0293.
- the GC analysis result of this fraction (purified pyridine) was as shown below.
- Impurity content Pyrazine ND (not measured), Pyrimidine ND, and 2-methylpyridine 43 mass ppm.
- Impurity content Triethylamine 0.07% by mass
- 2-methylpyrazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a reagent 2-methylpyridine (manufactured by Kanto Chemical Co., Inc.) having a purity of 99.7% by mass, and 2-methylpyrazine containing 27 mass ppm of 2-methylpyrazine was added.
- a pyridine solution was prepared.
- 2-methylpyrazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to reagent 3-methylpyridine (manufactured by Wako Pure Chemical Industries, Ltd.) having a purity of 99.8% by mass, and 3 mass ppm of 2-methylpyrazine was contained.
- reagent 3-methylpyridine manufactured by Wako Pure Chemical Industries, Ltd.
- the present invention provides a method for producing a high-purity pyridine compound from a crude pyridine compound with very little diazine compound.
- the pyridine compound produced by the method of the present invention can be used as an organic synthetic material, a chemical, a raw material for agricultural chemicals, a solvent for reaction, and a cleaning solvent.
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Abstract
Description
ピリジン化合物に紫外線を照射した後蒸留を行う方法(特許文献1)、
ピリジン化合物を塩素、臭素、ヨウ素等のハロゲンで処理する方法(特許文献2)、
酸と塩を形成させた後活性炭で処理する方法(特許文献3)、
ハロゲン含有硫黄またはリン化合物で処理する方法(特許文献4)、
イソシアネート類で処理する方法(特許文献5)、
メタノール、水を加え蒸留する方法(特許文献6)、
多孔質樹脂と接触処理する方法(特許文献7)、
アルカリ土類金属酸化物もしくは水酸化物で処理する方法(特許文献8)、
気相で固体アルカリ処理する方法(特許文献9)、
過マンガン酸塩もしくは重クロム酸塩で処理し蒸留する方法(特許文献10)、および
金属銅または酸化銅と加熱した後蒸留する方法(特許文献11)。
以上の事情は、他のピリジン化合物でも同様である。もう一つの例としてメチルピリジン(ピコリン)、メチルピラジン、およびメチルピリミジンの標準沸点を表2に比較した。
共にNaNH2等とは炭素上で求核置換反応を起こし、それぞれアミノピリジンおよびアミノピラジンを与える。
過酸化水素等により酸化を受け、対応するN-オキシドとなる。還元に関しては、完全に還元されると、それぞれピペリジンおよびピペラジンとなる。
ピリジン化合物およびジアジン化合物の化学的性質についてはこれまで様々調べられてきている。しかしながら、これを利用したピリジン化合物からそこに含まれるジアジン化合物の不純物を除く簡便な精製方法はこれまで知られていない。
また、本発明の他の一態様に係るピリジンは、99.9質量%以上のピリジンを含み、320nmにおける単位長あたりの吸光度が0.04cm-1以下である。
かかる製造方法によれば、不純物であるジアジン化合物の含有量が非常に小さく、ピリジンの純度が特に高いピリジン化合物を得ることができる。表1および2に示すように、特にピリジン化合物とピラジン化合物およびピリミジン化合物は標準沸点が近く蒸留で分離することは難しい場合が多い。さらにピラジン化合物は320nm付近に比較的強いUV吸収ピークを持っており、これらが不純物として含まれるとUV吸収の性質に大きな影響を与える。本発明によれば、このような不純物に由来するUV吸収が極めて低く、ピリジンの純度が特に高いピリジン化合物を得ることができる。
本発明の一実施形態に係るピリジン化合物の製造方法は、粗製ピリジン化合物を水素化アルミニウム化合物と反応させる反応ステップと、この反応ステップにより得られた反応物を蒸留する蒸留ステップとを有することを特徴とする。
(一般式(1)中、Aはアルカリ金属、pは0、1、2、または3のいずれかであり、R1はアルキル基、または内部に一つのエーテル基を持つアルコキシアルキル基である)。
(式中、R2およびR3は、それぞれ独立に水素またはアルキル基である)。
AlHR2R3(NR4R5R6)n (3)
(式中、R2およびR3は、それぞれ独立に水素またはアルキル基であり、nは1または2のいずれかであり、R4、R5およびR6は、それぞれ独立に水素、アルキル基またはアルケニル基のいずれかである。さらに、R4、R5およびR6の内2つまたは全ては連結していても良い)。
(分析方法)
本発明における分析方法を以下に示した。
(株)島津製作所製GC-2014 GC装置を用いて測定を行った。
測定条件は以下のとおりである:
・キャリアガス: ヘリウム(He)、全流量 36.7mL/min、
・スプリット比: 50:1
・カラム: DB-WAX(30m×0.25mmID、0.15μm film)、
・カラム温度: 温度(時間)=50℃(0~10分)、50→80℃(10→20分)、80℃(20~40分)、
・検出方法: FID、
・気化室温度、検出器温度: 150℃、
・試料: オートインジェクターAOC-20iを使用し、2.0μLを注入、
・検出限界:GCチャートのノイズレベルの2倍のピーク高さに対する濃度を検出限界とした。
(2)1H NMR分析
日本電子(株)製JNM-ECS400 400MHz FT-NMR装置を用いて測定した。重クロロホルムを溶媒とし、同時に加えたTMSの信号を化学シフトの標準とした。
試料を内寸1cm角の石英セルに入れ、(株)島津製作所製UV-1700ダブルビーム紫外可視分光光度計を用いて測定を行った。測定直前に、測定側および参照側ともに純水を置いてゼロ補正を行った。特にこの状態で320nmでの吸光度がゼロであることを確認した。その後、純水を参照側として測定を行った。
上記の条件でGC測定を行い、得られたピーク面積から絶対検量線法にて定量した。
(5)水分測定
三菱化学(株)製KF-05カールフィッシャー型水分計を用い測定した。滴定剤および脱水溶媒として、アクアミクロン滴定剤SS1mgおよびアクアミクロン脱水溶媒CP(いずれも三菱化学(株)製)を使用した。
A)合成ピリジン・ロット1
UV: 320nm吸光度=0.2640
不純物含有量:
ピラジン 21質量ppm、および
ピリミジン 16質量ppm。
B)合成ピリジン・ロット2
UV: 320nm吸光度=0.3027
不純物含有量:
ピラジン 22質量ppm、および
ピリミジン 57質量ppm。
C)試薬ピリジン:和光純薬工業(株)製
UV: 320nm吸光度=0.0524
不純物含有量:
ピリミジン 6質量ppm、および
2-メチルピリジン 49質量ppm。
(比較例1)
49.1gの合成ピリジン・ロット1に2.0gの水素化カルシウム(関東化学(株)製)を添加してスラリーを得た。このスラリーを30分室温で攪拌した後、常圧で単蒸留を行った。加熱はオイルバスで行い、150℃に設定した。また、トップ温度は112~116℃であった。単蒸留により17.2g(35.0%)の留分を得た。得られた留分のUV測定を行った。その結果、320nmの吸光度に改善は見られなかった。
UV: 320nm吸光度=0.2661
不純物含有量:
ピラジン 17質量ppm、および
ピリミジン 12質量ppm。
ピラジン ND(測定されず)、
ピリミジン ND、および
2-メチルピリジン 43質量ppm。
(調製例)トリエチルアミンアランAlH3(NEt3)の調製
窒素気流下、7.6g(200mmol)のLiAlH4を250mLのヘキサンに懸濁させてスラリーを得た。このスラリーを15℃に冷却し、温度が上がらないよう注意しながら、27.5g(200mmol)のトリエチルアミン塩酸塩をスラリーに少しずつ加えた。全てのトリエチルアミン塩酸塩をスラリーに添加して得られた反応液を1時間攪拌した。その後、反応液の入ったフラスコをグローブボックス内に移し、グローブボックス内で反応液を濾過した。得られた濾液から溶媒を留去させることにより、無色透明液体のトリエチルアミンアランを得た(収量21.4g)。
結果をまとめて表4に示す。
本発明の方法により製造したピリジン化合物は、有機合成物質、薬品、農薬の原料、反応時の溶媒、ならびに洗浄用溶剤に用いることができる。
Claims (10)
- 粗製ピリジン化合物を水素化アルミニウム化合物と反応させる反応ステップと、この反応ステップにより得られた反応物を蒸留する蒸留ステップとを有することを特徴とするピリジン化合物の製造方法。
- 粗製ピリジン化合物の不純物がジアジン化合物を含む請求項1に記載のピリジン化合物の製造方法。
- ジアジン化合物がピラジン化合物およびピリミジン化合物からなる群から選ばれる一種または二種以上の化合物を含む請求項2記載のピリジン化合物の製造方法。
- ピリジン化合物がピリジン、モノアルキルピリジン、およびジアルキルピリジンからなる群から選ばれる一種または二種以上からなり、ジアジン化合物がピラジン、モノアルキルピラジン、ジアルキルピラジン、ピリミジン、モノアルキルピリミジン、およびジアルキルピリミジンからなる群から選ばれる一種または二種以上を含む請求項1から3のいずれかに記載のピリジン化合物の製造方法。
- 水素化アルミニウム化合物が、一般式(1)および(2)のいずれかで表される化合物を含む請求項1から4のいずれかに記載のピリジン化合物の製造方法:
A[AlH4-p(OR1)p] (1)
(一般式(1)中、Aはアルカリ金属、pは0、1、または2のいずれかであり、R1は炭素数1~6のアルキル基、または途中に一つのエーテル基を持つ総炭素数1~6のアルコキシアルキル基である。)
AlH3(NR2R3R4)n (2)
(一般式(2)中、nは1または2であり、R2、R3、およびR4は、水素または置換基であり、それぞれ異なっていても同じでも良く、またその内2つまたは全てが連結していても良い。) - 水素化アルミニウム化合物が、水素化リチウムアルミニウムおよび水素化ナトリウムアルミニウムの一種または二種である請求項1から5のいずれかに記載のピリジン化合物の製造方法。
- 請求項1から6に記載のいずれかの方法で製造されたピリジン化合物。
- 99.9質量%以上のピリジンを含み、ピラジン化合物の含有量が3質量ppm未満、かつピリミジン化合物の含有量が2質量ppm未満であるピリジン化合物。
- 99.9質量%以上のピリジンを含み、320nmにおける単位長あたりの吸光度が0.04cm-1以下であるピリジン化合物。
- 請求項1から6に記載のいずれかの方法で製造された請求項8または9に記載のピリジン化合物。
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EP09844925.9A EP2433930B1 (en) | 2009-05-22 | 2009-05-22 | Method for producing pyridine compound and pyridine compound |
KR1020117029780A KR101610991B1 (ko) | 2009-05-22 | 2009-05-22 | 피리딘 화합물의 제조방법 및 피리딘 화합물 |
JP2011514264A JP5142345B2 (ja) | 2009-05-22 | 2009-05-22 | ピリジン化合物の製造方法 |
CN200980159412.7A CN102448935B (zh) | 2009-05-22 | 2009-05-22 | 吡啶化合物的制备方法以及吡啶化合物 |
PCT/JP2009/059406 WO2010134193A1 (ja) | 2009-05-22 | 2009-05-22 | ピリジン化合物の製造方法およびピリジン化合物 |
US13/265,005 US8742128B2 (en) | 2009-05-22 | 2009-05-22 | Process for producing pyridine compound, and pyridine compound |
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US9255324B2 (en) * | 2012-08-15 | 2016-02-09 | Up Chemical Co., Ltd. | Aluminum precursor composition |
KR101652750B1 (ko) | 2015-12-03 | 2016-08-31 | 김종선 | 피리딘 및 그 유도체의 정제방법 |
KR101686081B1 (ko) * | 2016-03-15 | 2016-12-13 | 덕산실업(주) | 전자재료용 고순도 피리딘의 생산방법 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52951B2 (ja) | 1973-05-09 | 1977-01-11 | ||
JPS52108976A (en) * | 1976-03-10 | 1977-09-12 | Koei Chemical Co | Method for purificating pyridine bases |
JPS52118472A (en) * | 1976-03-29 | 1977-10-04 | Koei Chemical Co | Preventive method of coloring of pyridine bases |
JPS60215670A (ja) | 1984-04-11 | 1985-10-29 | Nippon Steel Chem Co Ltd | ピリジン塩基類の精製方法 |
JPS61251662A (ja) * | 1985-04-30 | 1986-11-08 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
JPS62129269A (ja) * | 1985-12-02 | 1987-06-11 | Sumikin Coke Co Ltd | ピリジン塩基類の精製法 |
JPH01261368A (ja) * | 1988-04-13 | 1989-10-18 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
JPH0272161A (ja) * | 1988-04-27 | 1990-03-12 | Nepera Inc | Uv級合成ピリジンの製造 |
JP2001199960A (ja) | 2000-01-13 | 2001-07-24 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
-
2009
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- 2009-05-22 WO PCT/JP2009/059406 patent/WO2010134193A1/ja active Application Filing
- 2009-05-22 JP JP2011514264A patent/JP5142345B2/ja active Active
- 2009-05-22 KR KR1020117029780A patent/KR101610991B1/ko active IP Right Grant
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52951B2 (ja) | 1973-05-09 | 1977-01-11 | ||
JPS52108976A (en) * | 1976-03-10 | 1977-09-12 | Koei Chemical Co | Method for purificating pyridine bases |
JPS5434736B2 (ja) | 1976-03-10 | 1979-10-29 | ||
JPS52118472A (en) * | 1976-03-29 | 1977-10-04 | Koei Chemical Co | Preventive method of coloring of pyridine bases |
JPS6019294B2 (ja) | 1976-03-29 | 1985-05-15 | 広栄化学工業株式会社 | ピリジン塩基類の着色防止法 |
JPS60215670A (ja) | 1984-04-11 | 1985-10-29 | Nippon Steel Chem Co Ltd | ピリジン塩基類の精製方法 |
JPS61251662A (ja) * | 1985-04-30 | 1986-11-08 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
JPH06746B2 (ja) | 1985-04-30 | 1994-01-05 | ダイセル化学工業株式会社 | ピリジンの精製方法 |
JPS62129269A (ja) * | 1985-12-02 | 1987-06-11 | Sumikin Coke Co Ltd | ピリジン塩基類の精製法 |
JPH0645597B2 (ja) | 1985-12-02 | 1994-06-15 | 住金化工株式会社 | ピリジン塩基類の精製法 |
JPH01261368A (ja) * | 1988-04-13 | 1989-10-18 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
JPH0272161A (ja) * | 1988-04-27 | 1990-03-12 | Nepera Inc | Uv級合成ピリジンの製造 |
JP2001199960A (ja) | 2000-01-13 | 2001-07-24 | Daicel Chem Ind Ltd | ピリジンの精製方法 |
Non-Patent Citations (4)
Title |
---|
"Comprehensive Heterocyclic Chemistry", vol. 3, 1984, PERGAMON PRESS |
DENNIS D. TANNER; CHI-MING YANG, J. ORG. CHEM., vol. 58, 1993, pages 1840 - 1846 |
KARL HENSEN ET AL., INORG. CHEM., vol. 38, 1999, pages 4700 - 4704 |
See also references of EP2433930A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014119292A1 (ja) * | 2013-01-31 | 2014-08-07 | 広栄化学工業株式会社 | ピリジン化合物の精製方法 |
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US20120041209A1 (en) | 2012-02-16 |
EP2433930B1 (en) | 2015-08-05 |
KR101610991B1 (ko) | 2016-04-08 |
CN102448935A (zh) | 2012-05-09 |
US8742128B2 (en) | 2014-06-03 |
EP2433930A4 (en) | 2013-08-21 |
KR20120023784A (ko) | 2012-03-13 |
CN102448935B (zh) | 2014-07-09 |
JP5142345B2 (ja) | 2013-02-13 |
EP2433930A1 (en) | 2012-03-28 |
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