JPS601305B2 - Method for producing 1-(4-pyridyl)pyridinium chloride - Google Patents
Method for producing 1-(4-pyridyl)pyridinium chlorideInfo
- Publication number
- JPS601305B2 JPS601305B2 JP12613278A JP12613278A JPS601305B2 JP S601305 B2 JPS601305 B2 JP S601305B2 JP 12613278 A JP12613278 A JP 12613278A JP 12613278 A JP12613278 A JP 12613278A JP S601305 B2 JPS601305 B2 JP S601305B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- ppc
- pyridyl
- pyridine
- producing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- DFOUTGGPUPHEMO-UHFFFAOYSA-N 2-pyridin-1-ium-4-ylpyridine;chloride Chemical compound Cl.N1=CC=CC=C1C1=CC=NC=C1 DFOUTGGPUPHEMO-UHFFFAOYSA-N 0.000 title claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 2
- IYYUWAULZBEIST-UHFFFAOYSA-N 4-pyridin-1-ium-1-ylpyridine Chemical compound C1=CC=CC=[N+]1C1=CC=NC=C1 IYYUWAULZBEIST-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- -1 chlorine-substituted pyridines Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- KKWRVUBDCJQHBZ-UHFFFAOYSA-N 3,4,5-trichloropyridine Chemical compound ClC1=CN=CC(Cl)=C1Cl KKWRVUBDCJQHBZ-UHFFFAOYSA-N 0.000 description 1
- UZUCHEKZABBQDF-UHFFFAOYSA-N 4-(2H-pyridin-1-yl)pyridine hydrochloride Chemical compound [Cl-].N1(CC=CC=C1)C1=CC=[NH+]C=C1 UZUCHEKZABBQDF-UHFFFAOYSA-N 0.000 description 1
- ZHXDEKGMEHBVFK-UHFFFAOYSA-M 4-pyridin-1-ium-1-ylpyridine;bromide Chemical compound [Br-].C1=CC=CC=[N+]1C1=CC=NC=C1 ZHXDEKGMEHBVFK-UHFFFAOYSA-M 0.000 description 1
- GEIZYPUHEGXPEQ-UHFFFAOYSA-M 4-pyridin-1-ium-1-ylpyridine;chloride Chemical compound [Cl-].C1=CC=CC=[N+]1C1=CC=NC=C1 GEIZYPUHEGXPEQ-UHFFFAOYSA-M 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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１一（４ーピリジル）ピリジニウムクロリド（
以下「ＰＰＣ」という）の製造法に係り更に詳しくはピ
リジンと塩素からＰＰＣを製造する方法の改良に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1-(4-pyridyl)pyridinium chloride (
The present invention relates to a method for producing PPC (hereinafter referred to as "PPC"), and more specifically relates to an improvement in a method for producing PPC from pyridine and chlorine.
ＰＰＣの望ましい工業的製法として「ピリジンを加熱下
に塩素と反応させる方法があり、従来この製法としては
ドイツ特許６１３４０２（１９３５）が知られている。A desirable industrial method for producing PPC is a method in which pyridine is reacted with chlorine under heating, and German Patent No. 613402 (1935) is known as this method.
この方法によれば塩素に対して２モル倍量のピリジンを
、クロロホルム又はオキシ塩化燐中、５０〜１５び０で
塩素又は少量の臭素を加えた塩素と反応させてＰＰＣ塩
酸塩（以下「ＰＰＣ・ＨＣＵという。）を得ている。ま
たＰＰＣ・ＨＣＩからＰＰＣを得る方法としては、民ｒ
．８９２９２１（１９５６）に、ＰＰＣ・ＨＣＩをメタ
ノールに溶解してアンモニアで中和し、析出する塩化ア
ンモニウムを炉別して、炉液を濃縮した後エーテルを加
えてＰＰＣを取得する方法が記されている。然しながら
、このＰＰＣ・ＨＣＩ製造法においては、３，４，５ー
トリクロルピリジン等の塩素置換ピリジン類が大量に副
生するので、ＰＰＣ・ＨＣＩの対塩素が約３０％（ＨＬ
Ｃ分析による）と低い。又この塩素置換ピリジン類は昇
華性のため反応装置のコンデンサーを閉塞する障害をお
こす。更に反応生成物は粘着性粒状結晶塊となるので取
扱が困難である。一方ＰＰＣを得る方法においては、Ｐ
ＰＣ・ＨＣＩの溶解、中和、副生物の炉過、濃縮等の繁
雑な工程を要する。本発明者らは、これら従来法の欠点
を改良して、容易に且つ収率よくＰＰＣを得る方法につ
いて鋭意研究を重ねた結果、過剰量のピリジンを塩素と
反応させれば、副生するＨＣＩがピリジン塩酸塩（以下
「Ｐｙ・ＨＣＵという。According to this method, pyridine in an amount of 2 times the mole of chlorine is reacted with chlorine or chlorine to which a small amount of bromine is added in chloroform or phosphorous oxychloride at a concentration of 50 to 15,000 chlorine.・HCU).In addition, as a method to obtain PPC from PPC/HCI,
．． 892921 (1956) describes a method for obtaining PPC by dissolving PPC/HCI in methanol, neutralizing it with ammonia, separating the precipitated ammonium chloride in a furnace, concentrating the furnace liquid, and then adding ether. However, in this PPC/HCI manufacturing method, a large amount of chlorine-substituted pyridines such as 3,4,5-trichloropyridine is produced as a by-product, so the chlorine content of PPC/HCI is approximately 30% (HL
C analysis) and low. In addition, the chlorine-substituted pyridines cause trouble by clogging the condenser of the reactor due to their sublimation properties. Furthermore, the reaction product becomes a sticky granular crystal mass that is difficult to handle. On the other hand, in the method of obtaining PPC, P
It requires complicated processes such as dissolving and neutralizing PC/HCI, filtering by-products, and concentrating. The present inventors have conducted intensive research on a method to improve the shortcomings of these conventional methods and obtain PPC easily and with high yield. As a result, the present inventors have found that if an excess amount of pyridine is reacted with chlorine, the by-product HCI is pyridine hydrochloride (hereinafter referred to as “Py・HCU”).
）となり製品がＰＰＣ・ＨＣＩではなくてＰＰＣとして
得られ、更に反応生成物を２ープロピルアルコールで処
理すれば、Ｐｙ・ＨＣＩのみが溶けるので容易にＰＰＣ
を分取できることを見出し、これら知見に基づいて本発
明をなすに到った。すなわち、本発明の方法は、加熱下
にピリジンを塩素もしくは塩素及び少量の臭素と反応さ
せてＰＰＣを製造する際に、塩素に対して２．５〜３．
５モル倍量のピリジンを反応させてＰＰＣを製造するこ
と、並びに該反応生成物を２−プロピルアルコールで処
理することによりＰＰＣを得ることからなっている。), the product is obtained as PPC instead of PPC/HCI, and if the reaction product is further treated with 2-propyl alcohol, only Py/HCI dissolves, so it can be easily converted into PPC.
We have found that it is possible to fractionate and have completed the present invention based on these findings. That is, in the method of the present invention, when producing PPC by reacting pyridine with chlorine or chlorine and a small amount of bromine under heating, the reaction ratio of pyridine to chlorine is 2.5 to 3.
It consists of producing PPC by reacting 5 molar amounts of pyridine, and obtaining PPC by treating the reaction product with 2-propyl alcohol.
本発明の方法によるＰＰＣ合成反応においては、ピリジ
ンは原料であると同時に反応溶媒及び副生するＨＣＩを
Ｐｙ・ＨＣＩとして捕捉するためのものであるから、過
剰量用いることが必要であるが、その量は塩素１モルに
対して２．５〜３．５倍モル、好ましくは約３倍モル用
いればよい。In the PPC synthesis reaction according to the method of the present invention, pyridine is not only a raw material but also a reaction solvent and a by-product to capture HCI as Py.HCI, so it is necessary to use an excess amount. The amount may be 2.5 to 3.5 times, preferably about 3 times, per mole of chlorine.
また該ピリジンに反応させる塩素は、単独でもよいが、
塩素に少量の臭素例えば２〜２０モル％好ましくは５〜
１０モル％を添加して用いるとＰＰＣの収率を約１５％
高めることができる。この臭素の添加方法としては塩素
と同時でも、臭素を添加した後塩素を吹込んでもよい。
但し臭素を添加した場合には、得られる製品はＰＰＣに
少量の１−（４ーピリジル）ピリジニウムブロミドが混
入した１−（４ーピリジル）ピリジニウムハラィドとな
る。約３倍モル量のピリジンに８０〜１４０午０好まし
〈は１００〜１２０ｑｏで塩素もしくは塩素及び臭素を
吹込んで反応させることにより得られた反応生成物はス
ラリー状になるから、約１００ｏＣで反応器から取出し
て冷却すれば、ＰＰＣはＰｙ・ＨＣＩと共に固化したも
のとして対塩素収率約８０％以上で得られる。また反応
生成物に２−プロピルアルコ−ルを使用塩素１モルに対
して約１００〜ｌ０００凧【加え、１〜５時間約７５〜
８３℃で還流させた後、室温まで徐冷して、ＰＰＣを析
出させることによって、Ｐｙ・ＨＣＩから分離されたＰ
ＰＣの結晶を得ることができる。このように、本発明の
方法によれば、容易にＰＰＣ合成収率を高めることがで
き、また反応生成物からは簡単な操作でＰＰＣを取出す
ことが可能になるので、本発明は、極めて望ましいＰＰ
Ｃの工業的製法を提供するものである。In addition, the chlorine to be reacted with the pyridine may be used alone, but
Chlorine with a small amount of bromine, e.g. 2-20 mol%, preferably 5-20 mol%
When used with the addition of 10 mol%, the yield of PPC can be increased to about 15%.
can be increased. Bromine may be added at the same time as chlorine, or chlorine may be added after bromine is added.
However, when bromine is added, the resulting product becomes 1-(4-pyridyl)pyridinium halide in which a small amount of 1-(4-pyridyl)pyridinium bromide is mixed into PPC. The reaction product obtained by blowing chlorine or chlorine and bromine (preferably 100 to 120 qo) into about 3 times the molar amount of pyridine becomes a slurry, so the reaction is carried out at about 100 oC. When taken out from the container and cooled, PPC can be obtained as a solidified product together with Py.HCI with a yield of about 80% or more based on chlorine. In addition, 2-propyl alcohol is used as a reaction product. Approximately 100 to 1,000 kites are used per mole of chlorine.
After refluxing at 83°C, PPC was separated from Py/HCI by slowly cooling to room temperature and precipitating PPC.
PC crystals can be obtained. As described above, according to the method of the present invention, it is possible to easily increase the PPC synthesis yield, and it is also possible to extract PPC from the reaction product with a simple operation, so the present invention is extremely desirable. PP
This provides an industrial method for producing C.
次に実施例によって本発明をさらに詳細に説明する。実
施例 １
１タフラスコにピリジン２３７ｇ（３モル）を仕込み１
１０ｏｏまで加溢したのち塩素７１ｇ（１モル）を５時
間にわたって吹込みその間の温度を１００〜１２０ｑｏ
に保った。Next, the present invention will be explained in more detail with reference to Examples. Example 1 1. Pyridine 237g (3 mol) was charged in a tough flask.
After flooding to 10oo, 71g (1 mol) of chlorine was blown in for 5 hours, and the temperature during that time was 100 to 120qo.
I kept it.
塩素を吹き込むにしたがって反応液が黒色を呈し、１−
（４−ピリジル）ピリジニウムクロリドの沈澱がスラリ
ー状で生成した。塩素吹き込み終了後冷却することによ
って固化した塊３０５．雛を得た。高速液体クロマトグ
ラフィーで分析したところ１−（４ーピリジル）ピリジ
ニゥムクロリドの純度は４７．５％であった。対塩素収
率７５．４％。実施例 ２
臭素鍵（０．０５モル）を入れたフラスコを経由して塩
素ガス６７．舵（０．９５モル）を、ピリジン２３ね（
３モル）を１１０℃まで加溢した中に５時間かけて吹き
込んだ。As chlorine was blown in, the reaction solution turned black, and 1-
A precipitate of (4-pyridyl)pyridinium chloride was formed in the form of a slurry. Mass 305 solidified by cooling after completion of chlorine blowing. I got a chick. Analysis by high performance liquid chromatography revealed that the purity of 1-(4-pyridyl)pyridinium chloride was 47.5%. Yield for chlorine: 75.4%. Example 2 Chlorine gas 67.5% was introduced via a flask containing bromine key (0.05 mol). rudder (0.95 mol), pyridine 23(
3 mol) was blown into the mixture over 5 hours at a temperature of 110°C.
すなわち塩素ガスに臭素ガスを同伴させながらピリジン
に吹き込んだ。この間の温度は１００〜１２０ｑｏに保
った。塩素吹き込み終了後冷却することによって固化し
た塊３０９．舷を得た。高速液体クロマトグラフィーで
分析したところ１−（４ーピリジル）ピリジニウムハラ
イド（ハライドの大部分はク。リドで少量のプロミドを
含む）の純度は５５．３％であった。対ハロゲン収率８
８．９％。実施例 ３
１クフラスコにピリジン２３７ｇ（３モル）を仕込み、
１１０『０まで加溢したのち塩素７１ｇ（１モル）を５
時間にわたって吹き込みその間の温度を１００〜１２０
℃に保った。That is, bromine gas was blown into pyridine while being accompanied by chlorine gas. The temperature during this time was maintained at 100 to 120 qo. Mass 309 solidified by cooling after completion of chlorine blowing. Gained shipboard. Analysis by high performance liquid chromatography revealed that the purity of 1-(4-pyridyl)pyridinium halide (the halide is mostly chloride and contains a small amount of bromide) was 55.3%. Yield to halogen 8
8.9%. Example 3 237 g (3 mol) of pyridine was charged in a 1-cup flask,
110 After flooding to 0, add 71 g (1 mol) of chlorine to 5
Blow over a period of time and keep the temperature between 100 and 120.
It was kept at ℃.
塩素を吹き込むにしたがって反応液が黒色を呈し１一（
４ーピリジル）ピリジニウムクロリドの沈澱がスラリー
状で生成した。塩素吹き込み終了後２ープロピルアルコ
ール２００泌を添加し２時間還流した。その後、２時間
かけて徐々に冷却し、ｉ９８．雌の析出結晶を得た。減
圧下６０ｏ０８時間乾燥することによって４−（１ーピ
リジル）ピリジニウムクロリドの結晶１６４．後を得た
。高速液体クロマトグラフィーで分析したところ純度は
８０．２％であった。収率は対塩素６８．４％であった
。なおこの結晶をエタノールに溶解し塩化水素ガスを吹
き込み生成する結晶をェタノ−ル溶媒で再結晶すること
によって融点１斑〜１６０℃の精製１一（４ーピリジル
）ピリジニウムクロリドヒド。クロリドが得られた。実
施例 ４
臭素滋（０．０５モル）を入れたフラスコを経由して塩
素ガス６７．趣（０．９５モル）を、ピリジン２３ね（
３モル）を１１０こ０まで加湿した中に５時間かけて吹
き込んだ。As chlorine was blown into the reaction solution, it turned black.
A precipitate of 4-pyridyl)pyridinium chloride was formed in the form of a slurry. After the chlorine injection was completed, 200 g of 2-propyl alcohol was added and the mixture was refluxed for 2 hours. Thereafter, the i98. Female precipitated crystals were obtained. Crystals of 4-(1-pyridyl)pyridinium chloride 164. were obtained by drying under reduced pressure for 60°C for 8 hours. I got the answer. When analyzed by high performance liquid chromatography, the purity was 80.2%. The yield was 68.4% based on chlorine. By dissolving this crystal in ethanol and blowing hydrogen chloride gas into it, the resulting crystal is recrystallized in an ethanol solvent to obtain purified 1-(4-pyridyl)pyridinium chloride hydride having a melting point of 1°C to 160°C. Chloride was obtained. Example 4 67% of chlorine gas was introduced via a flask containing bromine (0.05 mol). (0.95 mol), pyridine 23 (
3 mol) was blown into the humidified water to 110°C over 5 hours.
すなわち塩素ガスに臭素ガスを同伴させながら、ピリジ
ンに吹き込んだ。この間の温度は１００〜１２０℃に保
った。反応生成物を実施例３と同様の操作で２−プロピ
ルアルコール処理を行うことによって１一（４ーピリジ
ル）ピリジニウムハラィド（ハラィドの大部分はクロリ
ドで少量のブロミドを含む）の結晶１９６．略を得た。
高速液体クロマトグラフィーで分析した結果純度は８３
．１％であた。収率は対ハロゲン８１．６％であった。
実施例 ５ピリジン７８２．１ｋ９（９，９００モル）
を２，０００そ反応槽に仕込み８０午０まで加溢し臭素
２６．４ｋ９（１６５モル）を３０分で滴下した。That is, bromine gas was blown into pyridine while being accompanied by chlorine gas. The temperature during this time was maintained at 100-120°C. The reaction product was treated with 2-propyl alcohol in the same manner as in Example 3 to obtain crystals of 1-(4-pyridyl)pyridinium halide (most of the halide is chloride and contains a small amount of bromide). I got a clue.
As a result of high performance liquid chromatography analysis, the purity was 83.
．． Warm at 1%. The yield was 81.6% based on halogen.
Example 5 Pyridine 782.1k9 (9,900 mol)
2,000 pieces of bromine were charged into a reaction tank, and the mixture was flooded until 80:00, and 26.4k9 (165 mol) of bromine was added dropwise over 30 minutes.
Claims (1)
素と反応させて１−（４−ピリジル）ピリジニウムクロ
リドを製造する方法において、塩素に対して２．５〜３
．５モル倍量のピリジンを反応させることを特徴とする
１−（４−ピリジル）ピリジニウムクロリドの製造方法
。 ２ 加熱下に塩素に対して２．５〜３．５モル倍量のピ
リジンを反応させる工程と、該反応生成物を２−プロピ
ルアルコールで処理する工程とより成る１−（４−ピリ
ジル）ピリジニウムクロリドの製造方法。[Claims] 1. A method for producing 1-(4-pyridyl)pyridinium chloride by reacting pyridine with chlorine or chlorine and a small amount of bromine under heating, wherein the
．． 1. A method for producing 1-(4-pyridyl)pyridinium chloride, which comprises reacting with 5 moles of pyridine. 2 1-(4-pyridyl)pyridinium, which consists of a step of reacting pyridine in an amount of 2.5 to 3.5 moles with respect to chlorine under heating, and a step of treating the reaction product with 2-propyl alcohol. Method for producing chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12613278A JPS601305B2 (en) | 1978-10-16 | 1978-10-16 | Method for producing 1-(4-pyridyl)pyridinium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12613278A JPS601305B2 (en) | 1978-10-16 | 1978-10-16 | Method for producing 1-(4-pyridyl)pyridinium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5559167A JPS5559167A (en) | 1980-05-02 |
| JPS601305B2 true JPS601305B2 (en) | 1985-01-14 |
Family
ID=14927452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12613278A Expired JPS601305B2 (en) | 1978-10-16 | 1978-10-16 | Method for producing 1-(4-pyridyl)pyridinium chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS601305B2 (en) |
-
1978
- 1978-10-16 JP JP12613278A patent/JPS601305B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5559167A (en) | 1980-05-02 |
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