JPS63156774A - Production of 2-chloropyridine - Google Patents
Production of 2-chloropyridineInfo
- Publication number
- JPS63156774A JPS63156774A JP30141286A JP30141286A JPS63156774A JP S63156774 A JPS63156774 A JP S63156774A JP 30141286 A JP30141286 A JP 30141286A JP 30141286 A JP30141286 A JP 30141286A JP S63156774 A JPS63156774 A JP S63156774A
- Authority
- JP
- Japan
- Prior art keywords
- pyridine
- chloropyridine
- mol
- halogenated hydrocarbon
- hydrocarbon solvent
- 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
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 48
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- -1 trichloroethylene, tetrachlorethylene Chemical group 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing 2-chloropyridine using pyridine as a raw material. 2-Chlorpyridine is very useful as a pharmaceutical and agrochemical intermediate.
（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
No. 075 proposes a method of chlorinating pyridine in a halogenated hydrocarbon solvent in the presence of water and under ultraviolet irradiation.
（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チ前後、また選択率も６７チ前後と低く、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ズ混入したり、
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
The selection rate is low at around 30 inches, and the selection rate is around 67 inches, which is the second goal.
- Other chlorinated products are produced in addition to chlorpyridine. These by-products, highly chlorinated products, are difficult to separate from 2-chloropyridine, and even if they are purified by ordinary distillation methods, they may contaminate the 2-chloropyridine as impurities, or
Or it may cause blockage of the distillation column.
そのため高純度の２−り四ルビリジンを得るには、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 highly pure 2-tetrarupyridine, complicated operations such as extraction are essential, and industrially, it is necessary to install an extraction device, etc., which has a major drawback as a process.
（発明が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（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
Ｋ、ピリジン１モルに対して１．５〜１［ｌＬＯ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 effects for solving the invention) The present inventors
The problems of the above reaction should be solved (as a result of intensive studies, pyridine was irradiated with ultraviolet rays in a water-containing halogenated hydrocarbon solvent, K was 1.5 to 1 [lLO mol/mol/mol/mol of pyridine)
The present invention was completed by discovering that 2-chloropyridine can be produced with high selectivity and high yield by blowing chlorine into the reactor at a specific rate of 1 hour.
以下本発明の詳細について説明する。The details of the present invention will be explained 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〜ＩＱ、０モル／時でア’）、１．５モ
ル／時以下であると収率９選択率共に低下し、１ｒ１．
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〜ＩＩＬＯ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 IQ per mole of pyridine, and if it is 0 mole/hour (A'), if it is less than 1.5 mole/hour, both the yield and selectivity will decrease, and 1r1 ．．
If it exceeds 0 mol/hour, it becomes difficult to use chlorine efficiently. Therefore, it is preferably 1.5 to IILO mol/hour. Generally, 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７〜２５
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（１５〜５モル倍である。Examples of the halogenated hydrocarbon used in the present invention include commonly used chloroform, carbon tetrachloride, trichloroethylene, tetrachlorethylene, etc., and can be appropriately selected and used. At that time, 7 to 25 to pyridine
It is preferable to use twice the molar amount. Further, the amount of water added to the halogenated hydrocarbon is preferably 10 to 5 times the mole of pyridine (15 to 5 times).
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
The temperature is maintained at up to 50°C, more preferably at around 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て説明するが、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) The present invention will be described below with reference to Examples, but the present invention is not limited only to these Examples.
実施例１
内容積３００−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１９５９、ピリジン７、
０９及び水１．５りを仕込み、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った。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裔層を分析した結果、得ら
れた２−クロルピリジンはエフ７りであり、収率は仕込
んだピリジンに対して５７．５ ％、転化率は同じくピ
リジンに対して８４．７ ％であった。Example 1 A thermometer, a chlorine blowing tube, a light source cooling tube made of Pyrex glass, and a cooling tube were attached to a glass reactor having an internal volume of 300 mm, and carbon tetrachloride 1959, pyridine 7,
09 and 1.5 liters of water, and the temperature inside the reactor was set to 75-7.
It was maintained at 6°C. Next, under ultraviolet irradiation with a high-pressure mercury lamp, chlorine gas was added at 1.9 mol/mol per mol of pyridine.
The reaction was carried out by blowing at a flow rate of 15 minutes. The reaction solution was divided into two layers, an aqueous layer and an organic layer. After neutralizing this reaction solution with an aqueous sodium hydroxide solution, the progeny layer was analyzed, and it was found that the obtained 2-chloropyridine was F7. The conversion rate was 57.5% based on the charged pyridine, and the conversion rate was 84.7% based on the same 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７０９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モルに対して五９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４．１３９含まれ
ており、収率は仕込んだピリジンに対して４１．１ ｆ
ｉ、転化率は８５．４チであった。Example 2 Into the reactor of the same equipment as in Example 1, 195 g of carbon tetrachloride,
Add pyridine 709 and 1.5g of water and set the temperature inside the vessel to 75.
It was held at ~76°C. Next, under ultraviolet irradiation using a high-pressure mercury lamp, chlorine gas was blown in at a flow rate of 59 mol/hour per 1 mol of pyridine for 15 minutes to carry out a reaction. After neutralizing the reaction solution with an aqueous sodium hydroxide solution, each layer was analyzed and it was found that the reaction solution contained 4.139 2-chloropyridine, and the yield was 41.1 f based on the charged pyridine.
i. The conversion rate was 85.4 h.
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、０９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８０
モル７時の流速で１５分吹き込んで反応を行った。反応
液を水酸化す） ＩＪ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．
２１ｇ含まれており、収率は仕込んだピリジンに対して
４１．９％、転化率は８α９チであった。Example 3 Into the reactor of the same equipment as in Example 1, 195 g of carbon tetrachloride,
Pyridine 7, 09 and 1.5 g of water were charged, and the temperature inside the vessel was maintained at 75 to 76°C. Then, under ultraviolet irradiation with a high-pressure mercury lamp, 80% chlorine gas was added to 1 mole of pyridine.
The reaction was carried out by blowing for 15 minutes at a flow rate of 7 hours molar. After neutralization with an aqueous IJ solution, analysis of each layer revealed that 2-chloropyridine was present in the reaction solution.
The yield was 41.9% based on the charged pyridine, and the conversion rate was 8α9%.
比較例
比較例としてピリジン１モルに対してα９７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１．２６９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２五１チであった。Comparative Example As a comparative example, the same procedure as in Example 1 was carried out except that the reaction was carried out by blowing chlorine into 1 mole of pyridine at a flow rate of α97 mol/hour. As a result, 2-chloropyridine was found in the reaction solution. The yield was 12.5% based on the charged pyridine, and the conversion rate was 2.51%.
Claims (1)
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。When producing 2-chloropyridine by reacting pyridine and chlorine in a water-containing halogenated hydrocarbon solvent under ultraviolet irradiation, chlorine is added at a rate of 1.5 to 10.0 mol/hour per 1 mol of pyridine. A method for producing 2-chloropyridine characterized by blowing.
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 true JPS63156774A (en) | 1988-06-29 |
| JPH0611759B2 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 |
|---|---|
| JPH0611759B2 (en) | 1994-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK2474517T3 (en) | PROCEDURE FOR MANUFACTURING THE TRICHLOR-1 PROP | |
| JP2013151435A (en) | Bis(1,1-dichloro-3,3,3-trifluoropropyl)ether and method for producing the same | |
| WO2018123301A1 (en) | Method for manufacturing sulfur tetrafluoride | |
| JPS63156774A (en) | Production of 2-chloropyridine | |
| JPS59204149A (en) | Method for purifying hexafluoroacetone hydrate | |
| EP0019804B1 (en) | Bromination of side chain of m-phenoxytoluene | |
| US5696269A (en) | Process for the preparation of chlorination derivatives of pyridine compounds and utilization of bis(trichloromethyl) sulfone in the process | |
| US11584702B2 (en) | Process for producing trifluoroiodomethane (CF3I) from trifluoroacetic anhydride (TFAA) | |
| US3140289A (en) | Process for preparing methyl pyridinium 2 aldoxime chloride | |
| US2062002A (en) | Treatment of unsaturated polyhalides | |
| JPH05255145A (en) | Synthesis of n-perfluorooctyl bromide | |
| JPH0717606B2 (en) | Method for separating chloropyridines | |
| JPS6219544A (en) | Production of 2,3-dichloro-1-propanol | |
| JPS63179861A (en) | Production of 2,6-dichloropyridine | |
| JPS6137748A (en) | Manufacture of pure hydrate of furol and hexafuroloacetone from hemiacetal | |
| KR100543694B1 (en) | A process for the preparation of 2-chloropyridine | |
| DK150853B (en) | METHOD OF PREPARING 6-CHLORO-BENZOXAZOLONE | |
| EP0310255A1 (en) | Production of carbonyl difluoride | |
| JPH0560460B2 (en) | ||
| JPH09278704A (en) | Production of monochloropinacolone | |
| JPH045657B2 (en) | ||
| JPS63280035A (en) | Production of trifluoromethyltoluene | |
| JPS6239549A (en) | Production of 3,4-difluoroaniline | |
| KR101325698B1 (en) | Method for efficient recycling of sodiumhalides from the coupling reaction of 4-halophthalic acid | |
| US3505010A (en) | Manufacture of ammonium bromide and carbon monoxide from polybromomethanes |