JPS60214775A - Separation of 3-picoline - Google Patents
Separation of 3-picolineInfo
- Publication number
- JPS60214775A JPS60214775A JP6831584A JP6831584A JPS60214775A JP S60214775 A JPS60214775 A JP S60214775A JP 6831584 A JP6831584 A JP 6831584A JP 6831584 A JP6831584 A JP 6831584A JP S60214775 A JPS60214775 A JP S60214775A
- Authority
- JP
- Japan
- Prior art keywords
- picoline
- active component
- mixture
- inclusion complex
- complex
- 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.)
- Granted
Links
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
Ｉ技術分野１
本発明は、３−ピコリンの包接錯体形成剤、および包接
錯体形成による３−ピコリンの分離法に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field 1 The present invention relates to an inclusion complex-forming agent for 3-picoline and a method for separating 3-picoline by forming an inclusion complex.
［発明の目的］
３−ピコリンは医薬・農薬原料や溶剤として有用な物質
であり、例えばタール分留のピコリン留分や、アセトア
ルデヒド、ホルムアルデヒド及びアンモニアから得られ
る。しｈ−Ｌ、このピコリン留分には、３−ピコリンと
沸点が接近した４−ピコリンや２，６−ルチジンが含ま
れるため、常法の蒸留手段によって３−ピコリンを分離
精製するのは非常に困難である。[Object of the Invention] 3-Picoline is a substance useful as a raw material for medicines and agricultural chemicals and as a solvent, and can be obtained, for example, from the picoline fraction of tar fractionation, acetaldehyde, formaldehyde, and ammonia. Since this picoline fraction contains 4-picoline and 2,6-lutidine, which have boiling points close to that of 3-picoline, it is extremely difficult to separate and purify 3-picoline by conventional distillation methods. It is difficult to
本発明者らは、３−ピコリンの効率的な分離精製法につ
いて鋭意研究を重ねた結果、次式で表わされる１、１，
６．’６−チトラフエニルー１，６−ノヒドロキシー２
，４−ヘキサノイン（以下、ジアセチレンジオールと称
す）をホスト化合物として用い、３−ピコリンと４−ピ
コリンとの混合物に作用させると、３−ピコリンとジア
セチレンジオールとの結晶性包接錯体か優先的に晶出す
ることを見出した。そして、晶出しな包接錯体を分離し
、加熱することにより高純度の３−ピコリンを回収する
ことに成功した。こうして、ホスト化合物としてジアセ
チレンジオールを用いる錯体形成を利用すれば、蒸留に
よる分離精製が困剣な、沸点か相互に近４１！ｌ、する
３−ピコリンと４−ピコリンの混合物から、少ないエネ
ルギーで容易かつ効果的に高純度の３−ピコリンを分離
回収できることを見出し、本発明を完成した。As a result of extensive research into efficient separation and purification methods for 3-picoline, the present inventors found that 1, 1,
6. '6-titraphenyl-1,6-nohydroxy-2
, 4-hexanoin (hereinafter referred to as diacetylene diol) is used as a host compound, and when it acts on a mixture of 3-picoline and 4-picoline, a crystalline inclusion complex of 3-picoline and diacetylene diol preferentially forms. We found that crystallization occurs. They succeeded in recovering highly pure 3-picoline by separating the crystallized inclusion complex and heating it. Thus, by utilizing complex formation using diacetylene diol as a host compound, the boiling points are close to each other and are difficult to separate and purify by distillation. The present invention has been completed based on the discovery that highly pure 3-picoline can be easily and effectively separated and recovered with less energy from a mixture of 3-picoline and 4-picoline.
［発明の構成１
即ち、本発明は、ジアセチレンジオールからなる３−ピ
コリンの包接錯体形成剤、および、３−ピコリン含有混
合物とジアセチレンジオールとを混合して、３−ピコリ
ンとジアセチレンジオールとの間で結晶性包接錯体を形
成させ、得られた結晶性包接錯体を分離し、該錯体から
３−ピコリンを分別回収することを特徴とする、３−ピ
コリンの分離方法である。[Configuration 1 of the Invention] That is, the present invention provides an inclusion complex forming agent for 3-picoline consisting of diacetylene diol, and a mixture containing 3-picoline and diacetylene diol to form a 3-picoline and diacetylene diol. This is a method for separating 3-picoline, which is characterized by forming a crystalline inclusion complex between the 3-picoline and the 3-picoline, separating the obtained crystalline inclusion complex, and separately recovering 3-picoline from the complex.
上記包接錯体形成剤は、３−ピコリンの分離方法以外に
、３−ピブノンを含有する成る物質から３−ピコリンを
除去して、該物質を精製する目的でも使用することかで
とる。In addition to the method for separating 3-picoline, the above-mentioned inclusion complex forming agent can also be used for the purpose of removing 3-picoline from a substance containing 3-pibnone and purifying the substance.
本発明方法を実施するには、３−ピコリン含有混合物に
ジアセチレンジオールを添加し、必要１こ応じてこれを
加熱して包接錯体化を完全に行なわせ、その後必要に応
して冷却し生じた結晶を分離採取する。得られる包接錯
体の組成は、通常ジアセチレンジオール：３−ピコリン
−１：、１〜２のモル比である。To carry out the process of the present invention, diacetylene diol is added to a mixture containing 3-picoline, which is optionally heated to complete the inclusion complexation, and then optionally cooled. Separate and collect the resulting crystals. The composition of the resulting inclusion complex is usually a molar ratio of diacetylene diol:3-picoline-1:1 to 2.
包接錯体を形成させる際のジアセチレンジオールの使用
量は、特に制限はないか、通常３−ピコリンに対して０
．１〜２倍モルの割合で用′Ｖする。There is no particular restriction on the amount of diacetylene diol used when forming an inclusion complex, or it is usually 0 to 3-picoline.
．． It is used at a ratio of 1 to 2 times the mole.
包接錯体化は溶媒の存在下でも実施できる。かかる溶媒
としでは低級アルコール、低級炭化水素、低級アルキル
エーテルなどが挙げられる。Inclusion complexation can also be carried out in the presence of a solvent. Examples of such solvents include lower alcohols, lower hydrocarbons, and lower alkyl ethers.
包接錯体化の反応温度は、３−ピコリンの沸点以下であ
れば特に限定はされなし）が、３−ピコリン及びジアセ
チレンジオール以外の成分中における包接錯体の溶解度
の点から、０〜５０℃の範囲内で行なうのが好ましい。The reaction temperature for inclusion complex formation is not particularly limited as long as it is below the boiling point of 3-picoline), but from the viewpoint of the solubility of the inclusion complex in components other than 3-picoline and diacetylene diol, the reaction temperature is 0 to 50. It is preferable to carry out the reaction within the range of °C.
包￥＆錯体化は３〜２４時間の反応時間で完結する。Encapsulation and complexation are completed within a reaction time of 3 to 24 hours.
３−ピコリン含有混合物中には、３−ピコリン以外の成
分として、ジアセチレンジオールと３−ピコリンの包接
錯体化を阻害するような成分を含まないことが望ましい
。また、」―記の成分としては、生成する包接錯体を容
易に溶解しなし・ものが好ましい。It is desirable that the 3-picoline-containing mixture does not contain any components other than 3-picoline that would inhibit the formation of an inclusion complex between diacetylene diol and 3-picoline. In addition, the components listed in "-" are preferably those that do not easily dissolve the clathrate complex formed.
こうして生成したジアセチレンジオールと３−ピコリン
との包接錯体の分離は、濾過等の固液分離により達成さ
れる。分離された包接錯体は必要に応じて再結晶化によ
り精製を行なう。再結晶化の際の溶媒は、包接錯体の溶
解度の面か呟例えばメタノール、エチルエーテル、Ｉ＋
−ヘキサン等から選ぶのか好ましい。Separation of the inclusion complex of diacetylene diol and 3-picoline thus produced is achieved by solid-liquid separation such as filtration. The separated inclusion complex is purified by recrystallization if necessary. The solvent for recrystallization may be methanol, ethyl ether, I+ due to the solubility of the inclusion complex, etc.
- It is preferable to choose from hexane, etc.
分離され、必要に応じて再結晶化により精製された包接
錯体から３−ピコリンを分別回収するには、例えば包接
錯体を５（］〜２００℃の範囲内で加熱し、必要に応じ
て減圧にして、３−ピコリンを留出させる。In order to separate and recover 3-picoline from the inclusion complex that has been separated and purified by recrystallization if necessary, for example, the inclusion complex is heated within the range of 5 (] to 200°C, and if necessary, Apply vacuum to distill out 3-picoline.
１作用効果１
本発明方法に従えば、従来、蒸留による分離精製が不可
能とされてきた３−ピコリンと４−ピコリンおよび／ま
たは２，６−ルチジンの混合物か呟高純度の３−ピコリ
ンが分別回収される。極めて工業的に右利な３−ピコリ
ンの分離法である。1 Effect 1 According to the method of the present invention, highly pure 3-picoline, which is a mixture of 3-picoline, 4-picoline and/or 2,6-lutidine, which has conventionally been considered impossible to separate and purify by distillation, can be obtained. It will be collected separately. This is an extremely industrially useful method for separating 3-picoline.
［実施態様１
以下、本発明の実施例を挙げて詳細に説明するが、本発
明はこれに限定されるものではない。[Embodiment 1] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
実施例１
ジアセチレンジオール１２８１３−ピコリン２．７ｇ、
及び４−ピコリン０．７ｇをメタノール４０ＩＪｅに溶
解し、２０℃で１２時間放置すると、無色プリズム状結
晶が析出した。析出した結晶を枦別腰メタノール４０Ｊ
で再結すると、無色プリズム状結晶が７．５ｇ得られた
。得られた結晶を、３０＋ｎｌｌｌＨｇの減圧下、１０
０℃に加熱すると、３−ピコリンカ１．１ｇ留出した。Example 1 2.7 g of diacetylene diol 12813-picoline,
When 0.7 g of 4-picoline and 4-picoline were dissolved in methanol 40IJe and left at 20° C. for 12 hours, colorless prismatic crystals were precipitated. Pour the precipitated crystals into methanol 40J.
Upon re-crystallization, 7.5 g of colorless prismatic crystals were obtained. The obtained crystals were heated under reduced pressure of 30+nllllHg for 10
When heated to 0°C, 1.1 g of 3-picolinker was distilled out.
この３−ピコリン純度は９９．９％であった。The purity of this 3-picoline was 99.9%.
特許出願人 広栄化学工業株式会社Patent applicant: Koei Chemical Industry Co., Ltd.
Claims (5)
ドロキシー２，４−へキサジインを有効成分とする３−
ピコリンの包接錯体形成剤。(1) 3- containing 1,1,6.6-tetraphenyl-1,6-cyhydroxy-2,4-hexadiyne as an active ingredient
Inclusion complex former for picoline.
するために用いるものである、特許請求の範囲第１項記
載の剤。(2) The agent according to claim 1, which is used for separating 3-picoline from a 3-picoline-containing mixture.
ラフェニル−１，６−シヒドロキシー２，４−ヘキサジ
インとを混合して、３−ピコリンと１゜１．６．６−テ
トラフェニル−１，６−シヒドロキシー２．４−ヘキサ
ジインとの間で結晶性包接錯体を形成させ、得られた結
晶性包接錯体を分離し、該錯体から３−ピコリンを分別
回収することを特徴とする、３−ピコリンの分離方法。(3) Mixing the 3-picoline-containing mixture and 1.1,6.6-tetraphenyl-1,6-cyhydroxy-2,4-hexadiyne, 3-picoline and 1°1.6.6-tetraphenyl -1,6-cyhydroxy-2,4-hexadiyne to form a crystalline inclusion complex, the resulting crystalline inclusion complex is separated, and 3-picoline is fractionally recovered from the complex. A method for separating 3-picoline.
にあたり、該錯体を加熱して３−ピコリンを留出させる
ことを特徴とする特許請求の範囲第３項記載の方法。(4) The method according to claim 3, characterized in that when 3-picoline is separated and recovered from the crystalline inclusion complex, the complex is heated to distill out 3-picoline.
ピコリンおよび／または２．６−ルチジンを主成分とす
る混合物である、特許請求の範囲第３または４項記載の
方法。(5) A mixture containing 3-picoline contains 3-picoline and 4-picoline.
The method according to claim 3 or 4, which is a mixture mainly consisting of picoline and/or 2,6-lutidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6831584A JPS60214775A (en) | 1984-04-04 | 1984-04-04 | Separation of 3-picoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6831584A JPS60214775A (en) | 1984-04-04 | 1984-04-04 | Separation of 3-picoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60214775A true JPS60214775A (en) | 1985-10-28 |
| JPH0519548B2 JPH0519548B2 (en) | 1993-03-17 |
Family
ID=13370260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6831584A Granted JPS60214775A (en) | 1984-04-04 | 1984-04-04 | Separation of 3-picoline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60214775A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037251A (en) * | 2015-05-22 | 2015-11-11 | 南京红太阳生物化学有限责任公司 | 3,5-dimethylpyridine purifying method |
-
1984
- 1984-04-04 JP JP6831584A patent/JPS60214775A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037251A (en) * | 2015-05-22 | 2015-11-11 | 南京红太阳生物化学有限责任公司 | 3,5-dimethylpyridine purifying method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0519548B2 (en) | 1993-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2003300943A (en) | Method of recovery for triethylamine | |
| JPS60214775A (en) | Separation of 3-picoline | |
| JPS62164672A (en) | Production of 1,2-dimethylimidazole | |
| JP3804210B2 (en) | Process for producing 2-hydroxy-4-methylthiobutanoic acid | |
| JP2007332050A (en) | Manufacturing method of optically active n-tert-butylcarbamoyl-l-tert-leucine | |
| JPS6193165A (en) | Method of separating and purifying quinaldine | |
| JPH0439448B2 (en) | ||
| JP4397990B2 (en) | Purification method of 3-alkylflavanonol derivatives | |
| US2950282A (en) | Method for separation and recovery of diazabicyclo-octane | |
| JPH09136876A (en) | Recovery of 2-cyano-3-methylpyridine | |
| JPH07242633A (en) | Production of 5-aminoethylaminomethyl-2-chloropyridine | |
| JPS6036439B2 (en) | Separation and recovery method for triethylenediamine | |
| JP2688855B2 (en) | Method for purifying benzylacetoxime | |
| US2447419A (en) | Preparation of diphenylacetonitrile | |
| JPH04145040A (en) | Production of dipentaerythritol | |
| JPS6365053B2 (en) | ||
| JPH04290857A (en) | Crystallization process | |
| JPH0210134B2 (en) | ||
| JP2770512B2 (en) | Method for purifying alkali metal salts of aminoethylsulfonic acid | |
| JPH01153679A (en) | Purification of isoquinoline | |
| JPH0680031B2 (en) | Method for separating dihydroxybenzoic acid isomers | |
| JPH05163168A (en) | Selective separation of 2,6-diisopropylnaphthalene | |
| KR20190092434A (en) | Process for preparing benzyl 4-amino-3-chloro-5-fluoro-6- (4-chloro-2-fluoro-3-methoxyphenyl) picolinate | |
| JPH08337546A (en) | Separation and purification of m-ethylphenol | |
| JPS5885873A (en) | Purification of 1,2,3,4,6,7,8,9-octahydrophenazine |