JPH0611759B2 - Method for producing 2-chloropyridine - Google Patents
Method for producing 2-chloropyridineInfo
- Publication number
- JPH0611759B2 JPH0611759B2 JP30141286A JP30141286A JPH0611759B2 JP H0611759 B2 JPH0611759 B2 JP H0611759B2 JP 30141286 A JP30141286 A JP 30141286A JP 30141286 A JP30141286 A JP 30141286A JP H0611759 B2 JPH0611759 B2 JP H0611759B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- pyridine
- chloropyridine
- chlorine
- reaction
- 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.)
- Expired - Lifetime
Links
Landscapes
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ピリジンを原料とする２−クロルピリジンの
製造法に関する。２−クロルピリジンは、医薬及び農薬
の中間体として非常に有用である。TECHNICAL FIELD The present invention relates to a method for producing 2-chloropyridine using pyridine as a raw material. 2-chloropyridine is very useful as an intermediate for medicines and agricultural chemicals.
（従来の技術） ２−クロルピリジンの製造法として、ピリジンを直接塩
素化する方法は公知である。例えば、特開昭５０−８８
０７５号公報では、水存在下ハロゲン化炭化水素溶媒
中、紫外線照射下にピリジンを塩素化する方法が提案さ
れている。(Prior Art) As a method for producing 2-chloropyridine, a method of directly chlorinating pyridine is known. For example, JP-A-50-88
In 075, a method of chlorinating pyridine in a halogenated hydrocarbon solvent in the presence of water under irradiation of ultraviolet rays is proposed.
（発明が解決するための問題点） しかしこの方法では２−クロルピリジンの収率が２０〜
３０％前後、また選択率も６７％前後と低く、目的の２
−クロルピリジン以外に他の塩素化物が生成する。これ
らの副生物である高塩素化物は、２−クロルピリジンと
の分離が困難で、これを通常の蒸留法によって精製して
も、２−クロルピリジン中に不純物として混入したり、
あるいは蒸留塔の閉塞を起こしたりする。(Problems to be solved by the invention) However, in this method, the yield of 2-chloropyridine is 20 to
The target rate is around 30% and the selectivity is low at around 67%.
-Other chlorinated compounds are formed besides chloropyridine. High chlorinated products, which are these by-products, are difficult to separate from 2-chloropyridine, and even if they are purified by a normal distillation method, they are mixed as impurities in 2-chloropyridine,
Alternatively, it causes the blockage of the distillation column.
そのため高純度の２−クロルピリジンを得るには、抽出
等の複雑な操作が必須であり工業的にも抽出装置等の設
置を要し、プロセスとしては大きな欠点を有する。Therefore, in order to obtain high-purity 2-chloropyridine, a complicated operation such as extraction is indispensable, and installation of an extraction device or the like is required industrially, and there is a major drawback in the process.
（発明を解決するための手段及び作用） 本発明者らは、前記反応の問題点を解決すべく鋭意検討
した結果、ピリジンを含水ハロゲン化炭化水素溶媒中紫
外線照射のもとに、ピリジン１モルに対して１．５〜１
０．０モル／時という特定の速度で塩素を吹き込み反応
させることにより高選択的かつ高収率で、２−クロルピ
リジンを製造できることを見い出し本発明を完成した。(Means and Actions for Solving the Invention) As a result of intensive studies to solve the above-mentioned problems of the reaction, the present inventors have found that 1 mol of pyridine was exposed to ultraviolet light in a hydrated halogenated hydrocarbon solvent containing pyridine. For 1.5 to 1
The inventors have found that 2-chloropyridine can be produced with high selectivity and high yield by blowing chlorine at a specific rate of 0.0 mol / hour for reaction, and completed the present invention.
以下本発明の詳細について説明する。The details of the present invention will be described below.
本発明における、塩素の吹き込み速度はピリジン１モル
に対して１．５〜１０．０モル／時であり、１．５モル
／時以下であると収率，選択率共に低下し、１０．０モ
ル／時を越えると効率の良い塩素の利用が困難となる。
従って好ましくは１．５〜１０．０モル／時である。通
常本発明の反応は５分〜１時間で完結できる。In the present invention, the blowing rate of chlorine is 1.5 to 10.0 mol / hr with respect to 1 mol of pyridine, and if it is 1.5 mol / hr or less, both the yield and the selectivity will decrease to 10.0. If it exceeds mol / hour, it becomes difficult to use chlorine efficiently.
Therefore, it is preferably 1.5 to 10.0 mol / hour. Usually, the reaction of the present invention can be completed in 5 minutes to 1 hour.
本発明で使用するハロゲン化炭化水素としては、通常使
われるクロロホルム，四塩化炭素，トリクロルエチレ
ン，テトラクロルエチレン等が挙げられ、適宜選択して
用いることができる。その際、ピリジンに対して７〜２
５モル倍用いるのが好ましい。また、ハロゲン化炭化水
素に添加する水の量はピリジンに対して、１０モル倍以
下好ましくは０．５〜５モル倍である。Examples of the halogenated hydrocarbon used in the present invention include commonly used chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene and the like, which can be appropriately selected and used. At that time, 7 to 2 relative to pyridine
It is preferable to use 5 molar times. Further, the amount of water added to the halogenated hydrocarbon is 10 mol times or less, preferably 0.5 to 5 mol times, relative to pyridine.
そして、本発明における反応温度は、通常は室温から１
５０℃まで、さらに好ましくは使用する溶媒の沸点付近
に維持して行う。The reaction temperature in the present invention is usually from room temperature to 1
It is carried out at a temperature of up to 50 ° C., more preferably while maintaining it near the boiling point of the solvent used.
（発明の効果） 本発明の方法を用いることにより、短時間に２−クロル
ピリジンを高選択的かつ高収率で製造できる。(Effects of the Invention) By using the method of the present invention, 2-chloropyridine can be produced in a short time with high selectivity and high yield.
（実施例） 以下、本発明を実施例によっで説明するが、本発明はこ
れら実施例のみに限定されるものではない。(Examples) Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
実施例１ 内容積３００mlのガラス製反応器に温度計，塩素吹き込
み管，パイレックスガラス製光源冷却管、冷却管を取り
付けこの反応器内に四塩化炭素１９５ｇ，ピリジン７．
０ｇ及び水１．５ｇを仕込み、反応器内温度を７５〜７
６℃に維持した。次いで高圧水銀燈による紫外線照射の
もとで塩素ガスをピリジン１モルに対して１．９モル／
時の流速で１５分吹き込んで反応を行つた。反応液は水
層と有機層の２．層に分かれており、この反応液を水酸
化ナトリウム水溶液にて中和後各層を分析した結果、得
られた２−クロルピリジンは３．７７ｇであり、収率は
仕込んだピリジンに対して３７．５％、転化率は同じく
ピリジンに対して８４．７％であった。Example 1 A glass reactor having an inner volume of 300 ml was equipped with a thermometer, a chlorine blowing tube, a Pyrex glass light source cooling tube, and a cooling tube, and 195 g of carbon tetrachloride and pyridine 7.
0 g and 1.5 g of water were charged and the temperature inside the reactor was adjusted to 75-7.
Maintained at 6 ° C. Next, chlorine gas was 1.9 mol / mol to 1 mol of pyridine under UV irradiation from a high pressure mercury lamp.
The reaction was carried out by blowing for 15 minutes at the current flow rate. The reaction solution consists of a water layer and an organic layer. The reaction solution was divided into layers, and the reaction solution was neutralized with an aqueous solution of sodium hydroxide. Then, each layer was analyzed. As a result, the amount of 2-chloropyridine obtained was 3.77 g, and the yield was 37. The conversion rate was 5%, and the conversion rate was 84.7% based on pyridine.
実施例２ 実施例１と同じ装置の反応器に、四塩化炭素１９５ｇ，
ピリジン７．０ｇ及び水１．５ｇを仕込み室内温度を７
５〜７６℃に保持した。次いで高圧水銀燈による紫外線
照射のもとで塩素ガスをピリジン１モルに対して３．９
モル／時の流速で１５分吹き込んで反応を行った。反応
液を水酸化ナトリウム水溶液にて中和後、各層を分析し
た結果反応液中には２−クロルピリジンが４．１３ｇ含
まれており、収率は仕込んだピリジンに対して４１．１
％、転化率は８５．４％であった。Example 2 In a reactor having the same apparatus as in Example 1, 195 g of carbon tetrachloride,
Pyridine 7.0g and water 1.5g were charged and the room temperature was adjusted to 7
Hold at 5-76 ° C. Next, chlorine gas was added to 3.9 mol per mol of pyridine under the irradiation of ultraviolet rays from a high-pressure mercury lamp.
The reaction was carried out by bubbling at a flow rate of mol / hour for 15 minutes. After neutralizing the reaction solution with an aqueous solution of sodium hydroxide, each layer was analyzed, and as a result, the reaction solution contained 4.13 g of 2-chloropyridine, and the yield was 41.1 based on the charged pyridine.
%, And the conversion rate was 85.4%.
実施例３ 実施例１と同じ装置の反応器に、四塩化炭素１９５ｇ，
ピリジン７．０ｇ及び水１．５ｇを仕込み、器内温度を
７５〜７６℃に保持した。次いで高圧水銀燈による紫外
線照射のもとで塩素ガスをピリジン１モルに対して８．
０モル／時の流速で１５分吹き込んで反応を行った。反
応液を水酸化ナトリウム水溶液にて中和後、各層を分析
した結果、反応液中には、２−クロルピリジンが４．２
１ｇ含まれており、収率は仕込んだピリジンに対して４
１．９％、転化率は８０．９％であった。Example 3 In a reactor having the same apparatus as in Example 1, 195 g of carbon tetrachloride,
Pyridine (7.0 g) and water (1.5 g) were charged, and the temperature inside the container was maintained at 75 to 76 ° C. Next, chlorine gas was added to 1 mol of pyridine under irradiation of ultraviolet rays from a high-pressure mercury lamp.
The reaction was carried out by bubbling at a flow rate of 0 mol / hour for 15 minutes. After neutralizing the reaction solution with an aqueous sodium hydroxide solution, each layer was analyzed, and as a result, 4.2 chloropyridine was found in the reaction solution.
1g was included, and the yield was 4 with respect to the charged pyridine.
The conversion rate was 1.9% and the conversion rate was 80.9%.
比較例 比較例としてピリジン１モルに対して０．９７モル／時
の流速で塩素を吹き込んで反応を行った他は実施例１と
同様な操作を行った結果、反応液中には２−クロルピリ
ジンが１．２６ｇ含まれており収率は仕込んだピリジン
に対して１２．５％、転化率は２３．１％であった。Comparative Example As a comparative example, the same operation as in Example 1 was carried out except that chlorine was blown into the reaction liquid at a flow rate of 0.97 mol / hour with respect to 1 mol of pyridine. 1.26 g of pyridine was contained, the yield was 12.5% based on the charged pyridine, and the conversion rate was 23.1%.
Claims (1)
溶媒中、紫外線照射下に反応させて、２−クロルピリジ
ンを製造するに際して、ピリジン１モルに対して１．５
〜１０．０モル／時の速度で塩素を吹き込むことを特徴
とする２−クロルピリジンの製法。1. When 2-chloropyridine is produced by reacting pyridine and chlorine in a water-containing halogenated hydrocarbon solvent under irradiation of ultraviolet rays, 1.5 mol per 1 mol of pyridine is used.
A method for producing 2-chloropyridine, which comprises blowing chlorine at a rate of -10.0 mol / hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30141286A JPH0611759B2 (en) | 1986-12-19 | 1986-12-19 | Method for producing 2-chloropyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30141286A JPH0611759B2 (en) | 1986-12-19 | 1986-12-19 | Method for producing 2-chloropyridine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63156774A JPS63156774A (en) | 1988-06-29 |
| JPH0611759B2 true JPH0611759B2 (en) | 1994-02-16 |
Family
ID=17896564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30141286A Expired - Lifetime JPH0611759B2 (en) | 1986-12-19 | 1986-12-19 | Method for producing 2-chloropyridine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611759B2 (en) |
-
1986
- 1986-12-19 JP JP30141286A patent/JPH0611759B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63156774A (en) | 1988-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0346612A1 (en) | Process for production of 1,1,1-trifluoro-2,2-dichloroethane | |
| JPH01313442A (en) | Production of vinyl chloride | |
| JPWO2009122940A1 (en) | Method for purifying pyridine and method for producing chlorinated pyridine | |
| RU2054407C1 (en) | Method for production of 1,1-dichlor-1-fluoroethane | |
| JPH0611759B2 (en) | Method for producing 2-chloropyridine | |
| JPS6052741B2 (en) | Manufacturing method of hexachloroacetone | |
| JPH10182516A (en) | Purification method of octafluorocyclobutane | |
| JPH0717606B2 (en) | Method for separating chloropyridines | |
| JPS5826733B2 (en) | Ensocaldehydono Seizouhouhou | |
| JP3882855B2 (en) | Method for producing alkylbenzoyl chloride | |
| CN111072554A (en) | Synthesis method of 4-bromo-2-chloro-6-methoxypyridine | |
| JPH05255145A (en) | Synthesis of n-perfluorooctyl bromide | |
| JP2897833B2 (en) | Method for producing 2-chloro-4-fluorophenol | |
| JPH07121910B2 (en) | Method for separating and purifying chloropyridines | |
| JPS6020385B2 (en) | Purification method of 2-chloropyridine | |
| JP2630577B2 (en) | Method for separating and purifying 2-chloropyridine | |
| JPS63179861A (en) | Production of 2,6-dichloropyridine | |
| JP3788482B2 (en) | Method for producing alkylbenzoyl chloride | |
| JP2559433B2 (en) | Method for producing chloropyridine | |
| US3971730A (en) | Chlorinating composition of chlorine monoxide in 1,1,1-trichloroethane | |
| EP1119534B1 (en) | Method for the preparation of 3-bromo-1,1,1-trifluoropropane | |
| US3575830A (en) | Beta-chlorination of alpha hydroxyisobutyric acid | |
| JPH0615483B2 (en) | Method for producing trifluoromethyltoluene | |
| JPH09227440A (en) | Production of 3,3-dichloro-1,1,1-trifluoropropan-2-one | |
| JPH0827058A (en) | Method for producing bromodifluoroacetic acid fluoride |