JPS6058753B2 - Method for producing 2-bromopyridine or its derivatives - Google Patents
Method for producing 2-bromopyridine or its derivativesInfo
- Publication number
- JPS6058753B2 JPS6058753B2 JP791578A JP791578A JPS6058753B2 JP S6058753 B2 JPS6058753 B2 JP S6058753B2 JP 791578 A JP791578 A JP 791578A JP 791578 A JP791578 A JP 791578A JP S6058753 B2 JPS6058753 B2 JP S6058753B2
- Authority
- JP
- Japan
- Prior art keywords
- bromopyridine
- derivative
- chloropyridine
- reaction
- derivatives
- 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
Links
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 20
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- SOHDPICLICFSOP-UHFFFAOYSA-N 2-bromo-6-methylpyridine Chemical compound CC1=CC=CC(Br)=N1 SOHDPICLICFSOP-UHFFFAOYSA-N 0.000 description 3
- GXZDYRYYNXYPMQ-UHFFFAOYSA-N 2-chloro-6-methylpyridine Chemical compound CC1=CC=CC(Cl)=N1 GXZDYRYYNXYPMQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000003930 2-aminopyridines Chemical class 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FITOHRKHSHRFGS-UHFFFAOYSA-N O[BrH](=O)(=O)O Chemical compound O[BrH](=O)(=O)O FITOHRKHSHRFGS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VLZLEPNAKIFDQJ-UHFFFAOYSA-N n-pyridin-2-ylnitramide Chemical class [O-][N+](=O)NC1=CC=CC=N1 VLZLEPNAKIFDQJ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 150000005762 2-bromopyridine Chemical class 0.000 description 1
- NQRMLXOCMRALQV-UHFFFAOYSA-N 2-chloro-3,4,5,6-tetramethylpyridine Chemical compound CC1=NC(Cl)=C(C)C(C)=C1C NQRMLXOCMRALQV-UHFFFAOYSA-N 0.000 description 1
- CKFAUGYTGXHEGN-UHFFFAOYSA-N 2-chloro-3,4,6-trimethylpyridine Chemical compound CC1=CC(C)=C(C)C(Cl)=N1 CKFAUGYTGXHEGN-UHFFFAOYSA-N 0.000 description 1
- HYULJNAYJIWKQA-UHFFFAOYSA-N 2-chloro-3,4-dimethylpyridine Chemical compound CC1=CC=NC(Cl)=C1C HYULJNAYJIWKQA-UHFFFAOYSA-N 0.000 description 1
- MBRSIVVDKJMNCS-UHFFFAOYSA-N 2-chloro-3,5,6-trimethylpyridine Chemical compound CC1=CC(C)=C(Cl)N=C1C MBRSIVVDKJMNCS-UHFFFAOYSA-N 0.000 description 1
- FGUVEKFEQISNDB-UHFFFAOYSA-N 2-chloro-3,5-dimethylpyridine Chemical compound CC1=CN=C(Cl)C(C)=C1 FGUVEKFEQISNDB-UHFFFAOYSA-N 0.000 description 1
- XUBFMNFNLIDSCP-UHFFFAOYSA-N 2-chloro-3,6-dimethylpyridine Chemical compound CC1=CC=C(C)C(Cl)=N1 XUBFMNFNLIDSCP-UHFFFAOYSA-N 0.000 description 1
- RKVUCIFREKHYTL-UHFFFAOYSA-N 2-chloro-3-methylpyridine Chemical compound CC1=CC=CN=C1Cl RKVUCIFREKHYTL-UHFFFAOYSA-N 0.000 description 1
- UIUDRIPPDPPWRR-UHFFFAOYSA-N 2-chloro-4,5-dimethylpyridine Chemical compound CC1=CN=C(Cl)C=C1C UIUDRIPPDPPWRR-UHFFFAOYSA-N 0.000 description 1
- COVGXNSRDOYAJD-UHFFFAOYSA-N 2-chloro-4,6-dimethylpyridine Chemical compound CC1=CC(C)=NC(Cl)=C1 COVGXNSRDOYAJD-UHFFFAOYSA-N 0.000 description 1
- MZVSTDHRRYQFGI-UHFFFAOYSA-N 2-chloro-4-methylpyridine Chemical compound CC1=CC=NC(Cl)=C1 MZVSTDHRRYQFGI-UHFFFAOYSA-N 0.000 description 1
- VXLYOURCUVQYLN-UHFFFAOYSA-N 2-chloro-5-methylpyridine Chemical compound CC1=CC=C(Cl)N=C1 VXLYOURCUVQYLN-UHFFFAOYSA-N 0.000 description 1
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NKSUTZRHLFWMMT-UHFFFAOYSA-N 6-chloro-2,3,4-trimethylpyridine Chemical compound CC1=CC(Cl)=NC(C)=C1C NKSUTZRHLFWMMT-UHFFFAOYSA-N 0.000 description 1
- YNPVNRJYHWHNSC-UHFFFAOYSA-N 6-chloro-2,3-dimethylpyridine Chemical compound CC1=CC=C(Cl)N=C1C YNPVNRJYHWHNSC-UHFFFAOYSA-N 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005752 bromopyridines Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
本発明は２−ブロモピリジンまたはその誘導体の製法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-bromopyridine or its derivatives.
さらに詳しくは２−クロロピリジンまたはその誘導体を
原料として２−ブロモピリジンまたはその誘導体を製造
する方法に関するものである。More specifically, the present invention relates to a method for producing 2-bromopyridine or a derivative thereof using 2-chloropyridine or a derivative thereof as a raw material.
２−ブロモピリジンまたはその誘導体は農薬等の原料と
して有用な化合物であり、その製法としては、（１）
２−ニトロアミノピリジン誘導体をΞ臭化リンと反応さ
せる方法（Ｒｏｃ２ｎｉｋｉＣｈｅｍｉｉ４１、（５）
９１７（１９６７）（２）ピリジン誘導体を３５０〜４
５０℃の温度で、臭素一塩素の混合ガスと反応させてハ
ロゲン化し、２−クロロピリジン誘導体と共に２−ブロ
モピリジン誘導体を得る方法（Ｊ０ｒｎａ１０ｆＨｅｔ
ａｒ０ｃｙｃ１ｉｃＣｈｅｍｉｓｔｒｙ４（３）、３７
７〜３８０（１９６７））さらには（３） ２−アミノ
ピリジン誘導体をサンドマイヤーの方法によりジアゾ化
した後、臭化水素と反応させて目的物を得る方法（Ｊｏ
ｕｒｎａｌｏｆＡＴｎｅｒｉｃａｎＣｈｅｍｉｃａｌＳ
ｏｃｉｔｙ７５、５２９８〜、（１９５３））等が知ら
れている。2-bromopyridine or its derivatives are useful compounds as raw materials for agricultural chemicals, etc., and their production methods include (1)
Method for reacting 2-nitroaminopyridine derivative with Ξphosphorus bromide (Roc2nikiChemii41, (5)
917 (1967) (2) Pyridine derivatives from 350 to 4
A method of halogenating by reacting with a mixed gas of bromine monochlorine at a temperature of 50°C to obtain a 2-bromopyridine derivative together with a 2-chloropyridine derivative (J0rna10fHet
ar0cyclicChemistry4(3), 37
7-380 (1967)) and (3) a method of diazotizing a 2-aminopyridine derivative by Sandmeyer's method and then reacting it with hydrogen bromide to obtain the desired product (Jo
urnalofATnericanChemicalS
ocity75, 5298~, (1953)) are known.
しカルながら（１）および（３）の方法では収率がいず
れも４０％前後と低く、また２−ニトロアミノピリジン
誘導体および２−アミノピリジン誘導体は共に高価であ
るため、これらを原料として使用することは工業的に不
利である。However, methods (1) and (3) both have low yields of around 40%, and both 2-nitroaminopyridine derivatives and 2-aminopyridine derivatives are expensive, so these are used as raw materials. This is industrially disadvantageous.
また、（２）の反応により２−ブロモピリジンを製造す
る方法を採用した場合には収率は８０％程度に向上する
が、反応液がタール化しており反応液から製品を分離精
製することが難かしく、さらには高温下でハロゲンと反
応させるため、特に工業的実施に当つては装置の材質を
選定しなければならないなどの難点がある。本発明者ら
は従来法のように高価な原料を使用せずに、比較的低い
反応温度で高い収率が得られ、しかも生成物の分離が容
易な２−ブロモピリジンまたはその誘導体の製法につい
て研究を重ねた結果、２−クロロピリジンまたはその誘
導体を脱水された有機媒体で臭化水酸と接触させ、生成
した反応液を所定の温度に冷却して結晶を析出せしめ、
この結晶を精製すれば高収率で２−ブロモピリジンまた
はその誘導体が得られることを知つて本発明に到達した
。さらに目的物を晶析、分離したあとの有機媒体を主と
する母液を循環再使用すれば一層経済的であることを見
出し本発明を完成した。すなわち本発明の要旨は、
゛）一゛Ｙ゛
一般式 （ここにＲ１〜Ｒ，はＨまた
はＣＨ３を表わす）で示される２−クロロピリジンまた
はその誘導体を脱水された有機媒体中で臭化水酸と接触
反応せしめ、当該反応液から２−ブロモピリジンまたは
その誘導体を晶析せしめる。In addition, when the method of producing 2-bromopyridine by reaction (2) is adopted, the yield improves to about 80%, but the reaction solution turns into tar, making it difficult to separate and purify the product from the reaction solution. Furthermore, since the reaction with halogen is carried out at high temperatures, there are difficulties in that, especially in industrial implementation, the material of the equipment must be selected. The present inventors have developed a method for producing 2-bromopyridine or its derivatives that does not require the use of expensive raw materials as in conventional methods, provides high yields at relatively low reaction temperatures, and is easy to separate the product. As a result of repeated research, 2-chloropyridine or its derivatives were brought into contact with hydroxybromic acid in a dehydrated organic medium, and the resulting reaction solution was cooled to a predetermined temperature to precipitate crystals.
The present invention was achieved based on the knowledge that 2-bromopyridine or its derivatives can be obtained in high yield by purifying this crystal. Furthermore, they found that it would be more economical to recycle and reuse the mother liquor, which consists mainly of an organic medium, after crystallizing and separating the target product, and completed the present invention. That is, the gist of the present invention is to prepare 2-chloropyridine or a derivative thereof represented by the general formula 1-Y (where R1 to R represent H or CH3) with water bromide in a dehydrated organic medium. A contact reaction is carried out with an acid, and 2-bromopyridine or a derivative thereof is crystallized from the reaction solution.
結晶を分離した後の母液は要すれば循環再使用し、一方
当該反応液から沖別した結晶をアルカリで溶解、中和し
、溶媒で抽出後蒸留して一般式 ゝｍｌイ にこに
Ｒ１〜Ｒ４はＨまたはＣＨ３を表わす）で示される２−
ブロモピリジンまたはそのメチル誘導体を製造する方法
である。The mother liquor after separating the crystals is recycled and reused if necessary, while the crystals separated from the reaction solution are dissolved and neutralized with an alkali, extracted with a solvent, and then distilled to obtain the general formula ゝmlii Nikoni R1 ~R4 represents H or CH3) 2-
This is a method for producing bromopyridine or its methyl derivative.
本発明で原料として用いる２−クロロピリジンまたはそ
のメチル誘導体とは Ｙ″什゛
一般式 （ここにＲ１〜Ｒ４はＨまた
はＣＨ３を表わず）で示される化合物であつて、その具
体例を示せば、２−クロロピリジン、２−クロロー３−
メチルピリジン、２−クロロー４−メチルピリジン、２
−クロロー５−メチルピリジン、２−クロロー６−メチ
ルピリジン、２−クロロー３，４−ジメチルピリジン、
２−クロロー３，５−ジメチルピリジン、２−クロロー
３，６−ジメチルピリジン、２−クロロー４，５−ジメ
チルピリジン、２−クロロー４，６−ジメチルピリジン
、２−クロロー５，６−ジメチルピリジン．２−クロロ
ー３，４，５−トリチチルピリジン、２−クロロー３，
４，６−トリメチルピリジン、２−クロロー３，５，６
−トリメチルピリジン、２−クロロー４，５，６−トリ
メチルピリジン、２−クロロー３，４，５，６−テトラ
メチルピリジンである。2-chloropyridine or its methyl derivative used as a raw material in the present invention is a compound represented by the general formula Y'' (where R1 to R4 do not represent H or CH3). 2-chloropyridine, 2-chloro3-
Methylpyridine, 2-chloro4-methylpyridine, 2
-chloro5-methylpyridine, 2-chloro6-methylpyridine, 2-chloro3,4-dimethylpyridine,
2-chloro 3,5-dimethylpyridine, 2-chloro 3,6-dimethylpyridine, 2-chloro 4,5-dimethylpyridine, 2-chloro 4,6-dimethylpyridine, 2-chloro 5,6-dimethylpyridine. 2-chloro 3,4,5-trititylpyridine, 2-chloro 3,
4,6-trimethylpyridine, 2-chloro3,5,6
-trimethylpyridine, 2-chloro4,5,6-trimethylpyridine, and 2-chloro3,4,5,6-tetramethylpyridine.
本発明ではこれら２−クロルピリジンまたはその誘導体
の１種を脱水された有機媒体に溶解し、これを７０℃以
上、溶媒の沸点以下の温度に維持して、臭化水酸ガスを
通じて反応させる。In the present invention, 2-chloropyridine or one of its derivatives is dissolved in a dehydrated organic medium, maintained at a temperature of 70° C. or higher and lower than the boiling point of the solvent, and reacted with hydroxybromic acid gas.
反応温度が７０℃以下では反応の進行が遅く、溶媒の沸
点以上の温度で反応させてもとくに支障はないが、加圧
状態に維持しなければならない。If the reaction temperature is 70° C. or lower, the reaction progresses slowly, and there is no particular problem if the reaction is carried out at a temperature higher than the boiling point of the solvent, but a pressurized state must be maintained.
有機媒体としてはトルエン、ク的レベンゼン、クロロホ
ルム、氷酢酸などを使用することができ、とくに氷酢酸
を用いると好ましい結果が得られる。原料と脱水された
有機媒体との量比はとくに限定されないが通常、原料１
に対して１０〜２鍾量部程度添加すればよい。原料を溶
解させた有機媒体中に臭化水酸ガスを原料に対して１〜
１０モル倍の範囲内で通気させ、通常１〜田時間反応さ
せる。生成した反応液を２０℃以下に冷却すると生成物
の塩が析出する。これを常法により淵別した後、水酸化
ナトリウム、水酸化カリウムのごときアルカリ水溶液を
結晶に加えて溶解、中和し、溶媒で抽出後、蒸留するこ
とにより純度の高い製品が得られる。また結晶を分離し
たあとの有機媒体を主とする母液は循環して再使用する
ことができる。本発明の方法によれば、比較的安価に入
手できる原料を使用するので経済であり、しかも結晶を
分離したあとの母液は循環使用できるので工業的に一層
有利である。As the organic medium, toluene, chlorobenzene, chloroform, glacial acetic acid, etc. can be used, and particularly preferable results are obtained when glacial acetic acid is used. Although the ratio of the raw material to the dehydrated organic medium is not particularly limited, it is usually
It is sufficient to add about 10 to 2 parts by weight. Hydrobromic acid gas is added to the organic medium in which the raw materials are dissolved at a rate of 1 to 10% per raw material.
Aeration is carried out within a range of 10 mole times, and the reaction is usually carried out for 1 to 1 hour. When the generated reaction solution is cooled to 20° C. or lower, the salt of the product is precipitated. After separating this by a conventional method, a highly pure product can be obtained by adding an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to the crystals to dissolve and neutralize the crystals, extracting with a solvent, and then distilling. Furthermore, the mother liquor, which is mainly composed of an organic medium, after separating the crystals can be recycled and reused. The method of the present invention is economical because it uses raw materials that are available at relatively low prices, and is even more industrially advantageous because the mother liquor after separating the crystals can be recycled.
実施例１
攪拌機、温度計、冷却管および臭化水素ガス導入管を備
えた内容積２１のガラス製反応器に、脱水された氷酢酸
１′と２−クロロピリジン５６．８ｑとを入れて溶解し
た。Example 1 Dehydrated glacial acetic acid 1' and 56.8q of 2-chloropyridine were placed in a glass reactor with an internal volume of 21 and equipped with a stirrer, a thermometer, a cooling tube, and a hydrogen bromide gas introduction tube, and dissolved therein. did.
反応器内を１１０′Ｃまで昇温した後、臭化水素ガスを
吹込んだ。臭化水素ガスの吹込みは７時間行ない、その
間に消費した量は１２２ｙであつた。反応終了後２０′
Ｃまで冷却し、析出する結晶を炉別した。結晶は湿つた
状態で１０１ｙあり、これを２５％苛性ソーダー水溶液
に溶解、中和し、溶媒で抽出した後、蒸留を行つた。そ
の結果５９．２ｙの２−ブロモピリジンと４．０ｙの未
反応２−クロロピリジンを得た。２−ブロモピリジンの
沸点は８８゜Ｃ／２３ＴｓｎＨｇであつた。After the temperature inside the reactor was raised to 110'C, hydrogen bromide gas was blown into the reactor. The hydrogen bromide gas was blown in for 7 hours, and the amount consumed during that time was 122y. 20' after completion of reaction
The mixture was cooled to C and the precipitated crystals were separated from the furnace. The crystals had a size of 101y when wet, and were dissolved in a 25% aqueous solution of caustic soda, neutralized, extracted with a solvent, and then distilled. As a result, 59.2y of 2-bromopyridine and 4.0y of unreacted 2-chloropyridine were obtained. The boiling point of 2-bromopyridine was 88°C/23TsnHg.
また前記ｐ液を常法により分析すると、２−ブロモピリ
ジン７．２ｙ１２−クロロピリジン３．４ｙを含んでい
た。従つて２−ブロモピリジンの収率は使用した２−ク
ロロピリジンに対して８４．１％であり、転化した２−
クロロピリジンに対しては９６．７％であつた。実施例
２内容積が３００ｍｔであること以外は実施例１と同じ
ガラス製反応器にクロロベンゼン１００ｃｃを入れ、こ
れに２−クロロピリジン５．７ｑを溶解した。Further, when the p solution was analyzed by a conventional method, it contained 7.2y of 2-bromopyridine and 3.4y of 12-chloropyridine. Therefore, the yield of 2-bromopyridine was 84.1% based on the 2-chloropyridine used, and the yield of 2-bromopyridine was 84.1% based on the 2-chloropyridine used.
For chloropyridine, it was 96.7%. Example 2 100 cc of chlorobenzene was placed in the same glass reactor as in Example 1 except that the internal volume was 300 mt, and 5.7 q of 2-chloropyridine was dissolved therein.
反応器内を１１０゜Ｃまて昇温した後、臭化水素ガスを
５時間かけて２０．３ｙ吹込んだ、反応中次第（３に結
晶が析出する。反応が終了した後反応液を１０℃に冷却
し結晶をｐ別した。実施例１と同様に分離し、常法によ
り分析した結果、結晶中には２−ブロモピリジン５．９
ｑ１２ークロロピリジン１．０ｙを含有していたが、戸
液中には２−ブロモピリジンおよび２−クロロピリジン
は殆んど含まれていなかつた。After raising the temperature inside the reactor to 110°C, hydrogen bromide gas was blown in for 20.3y over 5 hours. The crystals were cooled to ℃ and separated.As a result of separation in the same manner as in Example 1 and analysis using a conventional method, it was found that 5.9% of 2-bromopyridine was present in the crystals.
Although it contained 1.0y of q12-chloropyridine, the solution contained almost no 2-bromopyridine and 2-chloropyridine.
従つて２−ブロモピリジンの収率は使用した２−クロロ
ピリジンに対して７５．２％であり、転化した２−クロ
ロピリジンに対しては９１．３％であつた。なお結晶分
離後の母液をクロルベンゼンと混合して使用し同様に反
応を行なわせたが何等の支障なく、ほぼ同様の収率を示
した。実施例３
原料として２−クロロー６−メチルピリジン５．４ｙを
用いた以外は実施例２と同じ方法で反応を行ない、常法
により分析した結果２−ブロモー６−メチルピリジン７
．１９、未反応の２−クロロー６−メチルピリジン０．
７ｇを含んでいた。The yield of 2-bromopyridine was therefore 75.2% based on the 2-chloropyridine used and 91.3% based on the converted 2-chloropyridine. The same reaction was carried out using the mother liquor after crystal separation mixed with chlorobenzene, and almost the same yield was obtained without any problems. Example 3 The reaction was carried out in the same manner as in Example 2 except that 5.4y of 2-bromo-6-methylpyridine was used as the raw material, and the result of analysis using a conventional method was 2-bromo-6-methylpyridine 7.
．． 19. Unreacted 2-chloro6-methylpyridine 0.
It contained 7g.
従つ″て２−ブロモー６−メチルピリジンの収率は８２
．３％であり、転化した２−クロロー６−メチルピリジ
ンに対して９２．４％であつた。実施例４〜７
原料に２−クロロピリジン誘導体を用いた以外・は、実
施例１と同様に氷酢酸１１を用いて反応を行なつた。Therefore, the yield of 2-bromo-6-methylpyridine is 82
．． 3%, and 92.4% based on the converted 2-chloro-6-methylpyridine. Examples 4 to 7 Reactions were carried out using glacial acetic acid 11 in the same manner as in Example 1, except that a 2-chloropyridine derivative was used as the raw material.
反応終了後、実施例１と同様に処理して目的物である２
−ブロモピリジン誘導体を得ることができた。その結果
を下表に示した。After the reaction, the desired product 2 was obtained by the same treatment as in Example 1.
- A bromopyridine derivative could be obtained. The results are shown in the table below.
Claims (1)
Ｒ＿１〜Ｒ＿４はＨまたはＣＨ＿３を表わす）で示され
る２−クロロピリジンまたは誘導体を脱水された有機媒
体中で臭化水素と接触反応せしめることを特徴とする一
般式▲数式、化学式、表等があります▼（ここにＲ＿１
〜Ｒ＿４はＨまたはＣＨ＿３を表わす）で示される２−
ブロモピリジンまたはその誘導体の製造法。 ２ ２−クロロピリジンまたは誘導体と臭化水素のモル
比が１：１〜１：１０である特許請求の範囲１記載の方
法。 ３ 脱水された有機媒体が氷酢酸である特許請求の範囲
１記載の方法。 ４ 当該反液から濾別した結晶をアルカリ水溶液で溶解
、中和し、溶媒で抽出後蒸留して製品を取得する特許請
求の範囲１記載の方法。 ５ 当該反応液から２−ブロモピリジンまたはその誘導
体を晶析、分離した後の母液を循環再使用する特許請求
の範囲１記載の方法。[Claims] 1. 2-chloropyridine or a derivative represented by the general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (where R_1 to R_4 represent H or CH_3) is odor-treated in a dehydrated organic medium. There are general formulas ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by a catalytic reaction with hydrogen chloride▼ (here R_1
~R_4 represents H or CH_3) 2-
A method for producing bromopyridine or a derivative thereof. 2. The method according to claim 1, wherein the molar ratio of 2-chloropyridine or derivative to hydrogen bromide is from 1:1 to 1:10. 3. The method of claim 1, wherein the dehydrated organic medium is glacial acetic acid. 4. The method according to claim 1, wherein the crystals filtered from the antiliquid are dissolved and neutralized in an aqueous alkaline solution, extracted with a solvent, and then distilled to obtain the product. 5. The method according to claim 1, wherein the mother liquor after crystallizing and separating 2-bromopyridine or its derivative from the reaction solution is recycled and reused.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP791578A JPS6058753B2 (en) | 1978-01-26 | 1978-01-26 | Method for producing 2-bromopyridine or its derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP791578A JPS6058753B2 (en) | 1978-01-26 | 1978-01-26 | Method for producing 2-bromopyridine or its derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54103873A JPS54103873A (en) | 1979-08-15 |
| JPS6058753B2 true JPS6058753B2 (en) | 1985-12-21 |
Family
ID=11678824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP791578A Expired JPS6058753B2 (en) | 1978-01-26 | 1978-01-26 | Method for producing 2-bromopyridine or its derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6058753B2 (en) |
-
1978
- 1978-01-26 JP JP791578A patent/JPS6058753B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54103873A (en) | 1979-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4127575A (en) | Preparation of chloro substituted pyridines | |
| JPS59144759A (en) | Preparation of 2-chloronicotinic acid | |
| JPS6058753B2 (en) | Method for producing 2-bromopyridine or its derivatives | |
| US4045429A (en) | 4-(4-Hydroxy- or acetoxy-3-carbomethoxyphenylazo)-benzenesulphonyl chloride | |
| EP0259663B1 (en) | Process for producing tetrafluorophihalic acid | |
| US4275212A (en) | Method of preparing pyridinyloxyphenols and derivatives | |
| JPH0822851B2 (en) | Method for producing 2,3,5-trichloropyridine | |
| CN104592101A (en) | New synthesis method of sodium 3,5,6-trichloropyridyl-2-alkoxide | |
| NO312027B1 (en) | Process for the preparation of O- (3-amino-2-hydroxypropyl) hydroxymic acid halides | |
| US3155674A (en) | Hydroxyiminomethyl | |
| US2800485A (en) | Method of making mono- | |
| JP2864653B2 (en) | Method for producing 2-hydroxynicotinic acid derivative | |
| JPH07304726A (en) | Preparation of 2-arylethanesulfonic acids | |
| JPS58964A (en) | Synthesis of 6-aminonicotic acid nicotinyl ester | |
| JPS6115848B2 (en) | ||
| US2948735A (en) | Process for the introduction of carboxyl groups into heterocyclic compounds | |
| KR100517343B1 (en) | Preparation method of Methoxyphenylhydrazine | |
| JP2001106672A (en) | Method for producing 2,5-dichloropyridine | |
| JPH07206821A (en) | Process for producing pyridines having chlorine atom in α position | |
| JPH023672A (en) | 2,6-diethylaniline derivative and production thereof | |
| JPS6127961A (en) | Preparation of n-substituted phthalimide | |
| JPS601309B2 (en) | Method for producing 4-chlorpyridine hydrochloride | |
| JPS6155503B2 (en) | ||
| JPH06192225A (en) | Production of 1@(3754/24)-4-pyridyl)piperazines | |
| JPS61151165A (en) | Production of polythiobisphenol |