JP2005139149A - Method for producing quinoline-8-sulfonyl chloride - Google Patents
Method for producing quinoline-8-sulfonyl chloride Download PDFInfo
- Publication number
- JP2005139149A JP2005139149A JP2003379986A JP2003379986A JP2005139149A JP 2005139149 A JP2005139149 A JP 2005139149A JP 2003379986 A JP2003379986 A JP 2003379986A JP 2003379986 A JP2003379986 A JP 2003379986A JP 2005139149 A JP2005139149 A JP 2005139149A
- Authority
- JP
- Japan
- Prior art keywords
- quinoline
- reaction
- mol
- sulfonyl chloride
- thionyl chloride
- 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.)
- Pending
Links
Abstract
Description
本発明は、キノリン−８−スルホニルクロライドの製造方法に関する。さらに詳しくは、医薬用原料として有用な高純度のキノリン−８−スルホニルクロライドを、工業的に有利に製造する方法に関する。 The present invention relates to a method for producing quinoline-8-sulfonyl chloride. More specifically, the present invention relates to a method for industrially advantageously producing a high purity quinoline-8-sulfonyl chloride useful as a pharmaceutical raw material.
従来、キノリン−８−スルホニルクロライドを製造する方法としては、キノリンを原料とする方法が知られている。例えば、（１）キノリンに、大過剰のクロロ硫酸を反応させる方法（非特許文献１）や（２） キノリンと発煙硫酸を反応させ、キノリンのスルホン化物を合成し、キノリンのスルホン化物と五塩化リンを反応させる方法（非特許文献２）が挙げられる。 Conventionally, as a method for producing quinoline-8-sulfonyl chloride, a method using quinoline as a raw material is known. For example, (1) a method of reacting quinoline with a large excess of chlorosulfuric acid (Non-patent Document 1) or (2) a reaction of quinoline and fuming sulfuric acid to synthesize quinoline sulfonated product, quinoline sulfonated product and pentachloride A method of reacting phosphorus (Non-patent Document 2) can be mentioned.
しかし、上記（１）の方法では、キノリンのスルホン化物が２０〜３０％生じてしまうため、収率が低下し、高純度品が得られないという欠点がある。 また、(２) の方法では、上述の欠点の他に、一度キノリンのスルホン化物として取り出さなければならないため、繁雑な操作と時間を要し、さらに毒性の強い五塩化リンを使用する必要があるなどの欠点がある。 However, in the method (1), sulfonated quinoline is produced in an amount of 20 to 30%, so that the yield is lowered and a high-purity product cannot be obtained. In addition, in the method (2), in addition to the above-mentioned drawbacks, it must be once taken out as a sulfonated product of quinoline. Therefore, it requires complicated operation and time, and it is necessary to use highly toxic phosphorus pentachloride. There are disadvantages such as.
一般にスルホニルクロライド化の反応性は目的物質によって大きく異なり、高純度のキノリン−８−スルホニルクロライドを製造するためのクロロ硫酸および塩化チオニルの使用方法、使用量、反応温度等の好適な条件は未だ見い出されてはいないのが現状である。 In general, the reactivity of the sulfonyl chloride varies greatly depending on the target substance, and suitable conditions such as the method of using chlorosulfuric acid and thionyl chloride, the amount used, and the reaction temperature for producing high purity quinoline-8-sulfonyl chloride have not yet been found. The current situation is not.
本発明の目的は、医薬用原料として有用な高純度のキノリン−８−スルホニルクロライドを、安全かつ、工業的に有利に製造する方法を提供することにある。 An object of the present invention is to provide a method for producing a highly pure quinoline-8-sulfonyl chloride useful as a pharmaceutical raw material in a safe and industrially advantageous manner.
本発明者らは、上記課題を達成すべくキノリンを原料とし、キノリン−８−スルホニルクロライドを製造する際のスルホニルクロライド化反応におけるクロロ硫酸および塩化チオニルの使用方法、使用量および反応温度と目的物の純度の関係について鋭意検討を重ねた結果、キノリンを原料とし、これにクロロ硫酸を用い、キノリンが実質的に消失するまで反応させ、キノリンのスルホン化物とキノリンのクロロスルホン化物との混合物としたのち、この混合物にジメチルホルムアミド存在下又は不存在下に塩化チオニルとを反応させることにより、目的物を高純度で得ることができることを見出し、本発明を完成するに至った。 In order to achieve the above object, the present inventors have used quinoline as a raw material, the method of using chlorosulfuric acid and thionyl chloride in the sulfonyl chloride reaction when producing quinoline-8-sulfonyl chloride, the amount used, the reaction temperature and the target product. As a result of intensive studies on the relationship between the purity of quinoline, quinoline was used as a raw material, and chlorosulfuric acid was used as a raw material, and the reaction was continued until quinoline substantially disappeared, resulting in a mixture of a quinoline sulfonate and a quinoline chlorosulfonate. Thereafter, it was found that the target product can be obtained with high purity by reacting this mixture with thionyl chloride in the presence or absence of dimethylformamide, and the present invention has been completed.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明においては、キノリンを原料とし、これにクロロ硫酸を用い、キノリンが実質的に消失するまで反応させ、キノリンのスルホン化物とキノリンのクロロスルホン化物との混合物としたのち、この混合物にジメチルホルムアミド存在下又は不存在下に塩化チオニルとを反応させることにより目的物を高純度で得ることができるのであって、それ以外の方法例えば、キノリンを原料とし、これにクロロ硫酸と塩化チオニルとの混合物を反応させた場合は、収率も低く、多種類の不純物を含み、目的物を高純度で得ることはできない。 In the present invention, quinoline is used as a raw material, chlorosulfuric acid is used as a raw material, and the quinoline is reacted until it substantially disappears to form a mixture of a quinoline sulfonated product and a quinoline chlorosulfonated product, and then dimethylformamide is added to the mixture. The target product can be obtained in high purity by reacting with thionyl chloride in the presence or absence, and other methods, for example, using quinoline as a raw material, and a mixture of chlorosulfuric acid and thionyl chloride When the reaction is carried out, the yield is low, it contains many kinds of impurities, and the target product cannot be obtained with high purity.
本発明におけるクロロ硫酸の使用量は、キノリン１モル当たり、通常、４〜１０モルの範囲を選ぶのが好ましく、更に好ましくは、５〜８モルの範囲である。クロロ硫酸の使用量が４モル未満では生成物の収率が低下して好ましくなく、１０モルを越えると生産性の面で、工業的製造方法としては好ましくない。 The amount of chlorosulfuric acid used in the present invention is usually preferably in the range of 4 to 10 mol, more preferably in the range of 5 to 8 mol, per mol of quinoline. If the amount of chlorosulfuric acid used is less than 4 mol, the yield of the product is lowered, and if it exceeds 10 mol, it is not preferable as an industrial production method in terms of productivity.
本発明におけるキノリンとクロロ硫酸との反応温度は、クロロ硫酸の使用量等により異なるが、１００℃〜１６０℃の温度範囲を選ぶのが好ましい。 The reaction temperature of quinoline and chlorosulfuric acid in the present invention varies depending on the amount of chlorosulfuric acid used, but it is preferable to select a temperature range of 100 ° C to 160 ° C.
本発明におけるキノリンとクロロ硫酸との反応時間としては、クロロ硫酸の使用量等により異なるが、５〜１５時間の範囲で選ぶのが好ましい。 The reaction time of quinoline and chlorosulfuric acid in the present invention varies depending on the amount of chlorosulfuric acid used, but is preferably selected within the range of 5 to 15 hours.
本発明のキノリンとクロロ硫酸との反応においてキノリンが実質的に消失するまで反応したことを確認する方法としては、ＨＰＬＣ等の一般の分析法が適用でき、反応液中のキノリンの含有量が０．５重量％以下であれば、塩化チオニルとの反応工程に移行してもさしつかえない。 As a method for confirming that quinoline has been reacted until it substantially disappears in the reaction of quinoline and chlorosulfuric acid of the present invention, a general analytical method such as HPLC can be applied, and the content of quinoline in the reaction solution is 0. If it is less than 5% by weight, it can be transferred to the reaction step with thionyl chloride.
本発明における塩化チオニルの使用量は、キノリンのスルホン化物とキノリンのクロロスルホン化物との混合物中のキノリンのスルホン化物の含有量により調整され、キノリンのスルホン化物１モル当たり、通常、１モル〜１０モルの範囲であり、好ましくは、１モル〜５モルの範囲である。塩化チオニルの使用量が、１モル未満では生成物の収率が低下し、１０モルを越えると生産性の面で、工業的製造方法としては好ましくない。 The amount of thionyl chloride used in the present invention is adjusted by the content of the quinoline sulfonated product in the mixture of the quinoline sulfonated product and the quinoline chlorosulfonated product, and usually 1 mol to 10 mol per 1 mol of the quinoline sulfonated product. It is the range of a mole, Preferably it is the range of 1 mol-5 mol. When the amount of thionyl chloride used is less than 1 mol, the yield of the product is lowered, and when it exceeds 10 mol, it is not preferable as an industrial production method in terms of productivity.
本発明におけるキノリンのスルホン化物とキノリンのクロロスルホン化物の混合物と塩化チオニルとの反応温度は、塩化チオニルの使用量等により異なるが、５０℃以上が好ましく、６０℃〜８０℃の温度の範囲が反応面でさらに好ましい。 In the present invention, the reaction temperature of the mixture of sulfonated quinoline and chlorosulfonated quinoline and thionyl chloride varies depending on the amount of thionyl chloride used, but is preferably 50 ° C or higher, and the temperature range of 60 ° C to 80 ° C is preferred. More preferable in terms of reaction.
本発明におけるキノリンのスルホン化物とキノリンのクロロスルホン化物との混合物と塩化チオニルとの反応時間としては、塩化チオニルの使用量等により異なるが、通常１〜１０時間の範囲で選ぶのが好ましく、３〜６時間がさらに好ましい。 The reaction time of the mixture of the sulfonated product of quinoline and the chlorosulfonated product of quinoline and thionyl chloride in the present invention varies depending on the amount of thionyl chloride used, etc., but it is usually preferably selected in the range of 1 to 10 hours. -6 hours are more preferred.
本発明において必要に応じて用いるジメチルホルムアミドの使用量は、塩化チオニルの使用量により調整されるが、塩化チオニル１モル当たり、通常、０．０１モル〜０．５モルの範囲であり、好ましくは０．０５モル〜０．３モルの範囲である。 The amount of dimethylformamide used as necessary in the present invention is adjusted by the amount of thionyl chloride used, and is usually in the range of 0.01 mol to 0.5 mol per 1 mol of thionyl chloride, preferably The range is from 0.05 mol to 0.3 mol.
本発明において塩化チオニルにジメチルホルムアミドを添加して反応した場合、添加しない場合に比べて、反応時間を短縮することができ、生産性の向上に寄与することができる。 In the present invention, when dimethylformamide is added to and reacted with thionyl chloride, the reaction time can be shortened and the productivity can be improved as compared with the case where dimethylformamide is not added.
本発明における反応終了後の反応生成物は、反応混合物を氷水などのスルホニルクロライドに対する難溶性溶媒中に注入してキノリン−８−スルホニルクロライドの沈殿を生成させ、生じた固体を濾過、分離する方法等により、単離することができる。 The reaction product after the completion of the reaction in the present invention is a method in which the reaction mixture is poured into a sparingly soluble solvent for sulfonyl chloride such as ice water to form a quinoline-8-sulfonyl chloride precipitate, and the resulting solid is filtered and separated. It can be isolated by such as.
上記反応生成物から単離して得られたキノリン−８−スルホニルクロライドは、そのままもしくは、さらに必要に応じて再結晶などの精製処理を行ったあと、医薬用原料として使用される。 The quinoline-8-sulfonyl chloride obtained by isolation from the above reaction product is used as a raw material for pharmaceuticals as it is or after further purification treatment such as recrystallization as necessary.
本発明におけるキノリンとクロロ硫酸との反応およびキノリンのスルホン化物とキノリンのクロロスルホン化物との混合物と塩化チオニルとの反応は、窒素等の不活性ガス気流下で行うことが純度を向上させる上で、さらに好ましい。 In order to improve the purity, the reaction of quinoline and chlorosulfuric acid in the present invention and the reaction of a sulfonated product of quinoline and a chlorosulfonated quinoline with thionyl chloride are carried out under an inert gas stream such as nitrogen. More preferred.
本発明の製造方法によって、高純度のキノリン−８−スルホニルクロライドを、安全に、かつ、工業的に有利に製造する方法を提供することができる。 The production method of the present invention can provide a method for producing high-purity quinoline-8-sulfonyl chloride safely and industrially advantageously.
次に、本発明を実施例に基づいて更に具体的に説明するが、本発明は、以下の記載例に限定されるものではない。また以下において特にことわりのないかぎり、％は重量％を示す。 Next, the present invention will be described more specifically based on examples, but the present invention is not limited to the following description examples. In the following, “%” means “% by weight” unless otherwise specified.
メカニカルスターラー、ジムロート冷却器を装置した反応容器に、クロロ硫酸を４８．０グラム（０．４１モル）仕込み、窒素気流下に攪拌しつつ、氷冷下でキノリンを７．８グラム（０．０６モル）仕込んだ。フラスコ内容物を攪拌しつつ、内温を１４０℃に昇温し、この温度で１０時間反応させた。この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが６３％とキノリン−８−スルホン酸が２７％生成しており、原料であるキノリンの残存量は０．１％以下であった。次に、内温を４０℃以下にまで降温し、塩化チオニルを１１．０グラム（０．０９モル）仕込み、フラスコ内容物を攪拌しつつ、内温を７０℃まで昇温し、この温度で４時間反応させた。反応終了後、この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが８８％とキノリン−８−スルホン酸が０．５％生成していた。反応混合物を氷水中に投入し、析出物を濾過後、乾燥し、純度９９．５％のキノリン−８−スルホニルクロライド１１.３９ｇを得た。（収率：８３％） A reaction vessel equipped with a mechanical stirrer and a Dimroth condenser was charged with 48.0 g (0.41 mol) of chlorosulfuric acid, and 7.8 g (0.06 g) of quinoline under ice cooling while stirring under a nitrogen stream. Mol) charged. While stirring the contents of the flask, the internal temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 10 hours. When the reaction solution at this time was analyzed by liquid chromatography, 63% of quinoline-8-sulfonyl chloride and 27% of quinoline-8-sulfonic acid were produced, and the remaining amount of quinoline as a raw material was 0.1%. It was the following. Next, the internal temperature is lowered to 40 ° C. or lower, 11.0 g (0.09 mol) of thionyl chloride is charged, and the internal temperature is raised to 70 ° C. while stirring the flask contents. The reaction was performed for 4 hours. After completion of the reaction, the reaction solution at this point was analyzed by liquid chromatography. As a result, 88% of quinoline-8-sulfonyl chloride and 0.5% of quinoline-8-sulfonic acid were produced. The reaction mixture was poured into ice water, and the precipitate was filtered and dried to obtain 11.39 g of quinoline-8-sulfonyl chloride having a purity of 99.5%. (Yield: 83%)
実施例１のメカニカルスターラー、ジムロート冷却器を装置した反応容器に、クロロ硫酸を４８．０グラム（０．４１モル）仕込み、窒素気流下に攪拌しつつ、氷冷下でキノリンを７．８グラム（０．０６モル）仕込んだ。フラスコ内容物を攪拌しつつ、内温を１４０℃に昇温し、この温度で８時間反応させた。この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが６１％とキノリン−８−スルホン酸が２９％生成しており、原料であるキノリンの残存量は０．１％以下であった。次に、内温を４０℃以下にまで降温し、ジメチルホルムアミドを０．５グラム（０．００７モル）、塩化チオニルを１０．０グラム（０．０８モル）仕込み、フラスコ内容物を攪拌しつつ、内温を７０℃まで昇温し、この温度で４時間反応させた。反応終了後、この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが８９％とキノリンスルホン酸が０．１％生成していた。この反応液につき実施例１と同様の処理を行い、純度９９．６％のキノリン−８−スルホニルクロライド１１．７７ｇを得た。（収率：８６％） The reaction vessel equipped with the mechanical stirrer and Dimroth condenser of Example 1 was charged with 48.0 g (0.41 mol) of chlorosulfuric acid and 7.8 g of quinoline under ice cooling while stirring under a nitrogen stream. (0.06 mol) was charged. While stirring the contents of the flask, the internal temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 8 hours. When the reaction liquid at this time was analyzed by liquid chromatography, 61% of quinoline-8-sulfonyl chloride and 29% of quinoline-8-sulfonic acid were produced, and the remaining amount of quinoline as a raw material was 0.1%. It was the following. Next, the internal temperature was lowered to 40 ° C. or lower, 0.5 g (0.007 mol) of dimethylformamide and 10.0 g (0.08 mol) of thionyl chloride were charged, and the contents of the flask were stirred. The internal temperature was raised to 70 ° C., and the reaction was carried out at this temperature for 4 hours. After completion of the reaction, the reaction solution at this point was analyzed by liquid chromatography. As a result, 89% of quinoline-8-sulfonyl chloride and 0.1% of quinoline sulfonic acid were produced. The reaction solution was treated in the same manner as in Example 1 to obtain 11.77 g of quinoline-8-sulfonyl chloride having a purity of 99.6%. (Yield: 86%)
メカニカルスターラー、ジムロート冷却器を装置した反応容器に、クロロ硫酸を４８．０グラム（０．４１モル）仕込み、窒素気流下に攪拌しつつ、氷冷下でキノリンを７．８グラム（０．０６モル）仕込んだ。フラスコ内容物を攪拌しつつ、内温を１４０℃に昇温し、この温度で１０時間反応させた。この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが６３％とキノリン−８−スルホン酸が２７％生成しており、原料であるキノリンの残存量は０．１％以下であった。次に、内温を４０℃以下にまで降温し、ジメチルホルムアミドを０．５グラム（０．００７モル）、塩化チオニルを３．６７グラム（０．０３モル）仕込み、フラスコ内容物を攪拌しつつ、内温を７０℃まで昇温し、この温度で１時間反応させた。反応終了後、この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが８８％とキノリン−８−スルホン酸が０．１％生成していた。この反応液につき、実施例１と同様の処理を行い、純度９９．４％のキノリン−８−スルホニルクロライド１１．５２ｇを得た。（収率：８４％） A reaction vessel equipped with a mechanical stirrer and a Dimroth condenser was charged with 48.0 g (0.41 mol) of chlorosulfuric acid and 7.8 g (0.06 g) of quinoline under ice cooling while stirring under a nitrogen stream. Mol) charged. While stirring the contents of the flask, the internal temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 10 hours. When the reaction solution at this time was analyzed by liquid chromatography, 63% of quinoline-8-sulfonyl chloride and 27% of quinoline-8-sulfonic acid were produced, and the remaining amount of quinoline as a raw material was 0.1%. It was the following. Next, the internal temperature was lowered to 40 ° C. or less, 0.5 g (0.007 mol) of dimethylformamide and 3.67 g (0.03 mol) of thionyl chloride were charged, and the contents of the flask were stirred. The internal temperature was raised to 70 ° C., and the reaction was carried out at this temperature for 1 hour. After completion of the reaction, the reaction solution at this point was analyzed by liquid chromatography. As a result, 88% of quinoline-8-sulfonyl chloride and 0.1% of quinoline-8-sulfonic acid were produced. This reaction solution was treated in the same manner as in Example 1 to obtain 11.52 g of quinoline-8-sulfonyl chloride having a purity of 99.4%. (Yield: 84%)
（比較例１）
メカニカルスターラー、ジムロート冷却器を装置した反応容器に、クロロ硫酸を４８．０グラム（０．４１モル）仕込み、窒素気流下に攪拌しつつ、氷冷下でキノリンを７．８グラム（０．０６モル）仕込んだ。フラスコ内容物を攪拌しつつ、内温を１４０℃に昇温し、この温度で３時間反応させた。この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが５８％とキノリン−８−スルホン酸が２２％生成しており、原料であるキノリンの残存量は１２％であった。この反応液につき、実施例１と同様の処理を行い、純度７５.５％のキノリン−８−スルホニルクロライド４．３４ｇを得た。（収率２４％）
(Comparative Example 1)
A reaction vessel equipped with a mechanical stirrer and a Dimroth condenser was charged with 48.0 g (0.41 mol) of chlorosulfuric acid and 7.8 g (0.06 g) of quinoline under ice cooling while stirring under a nitrogen stream. Mol) charged. While stirring the contents of the flask, the internal temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 3 hours. The reaction solution at this point was analyzed by liquid chromatography. As a result, 58% of quinoline-8-sulfonyl chloride and 22% of quinoline-8-sulfonic acid were produced, and the remaining amount of quinoline as a raw material was 12%. It was. This reaction solution was treated in the same manner as in Example 1 to obtain 4.34 g of quinoline-8-sulfonyl chloride having a purity of 75.5%. (Yield 24%)
（比較例２）
メカニカルスターラー、ジムロートのを装置した反応容器に、クロロ硫酸を４８．０グラム（０．４１モル）と塩化チオニルを１１．０グラム（０．０９モル）仕込み、窒素気流下に攪拌しつつ、氷冷下でキノリンを７．８グラム（０．０６モル）仕込んだ。フラスコ内容物を攪拌しつつ、内温を１４０℃に昇温し、この温度で１０時間反応させた。この時点での反応液を液体クロマトグラフィーで分析したところキノリン−８−スルホニルクロライドが６２％とキノリン−８−スルホン酸が１０％生成しており、原料であるキノリンの残存量は０．１％以下であった。この反応液につき、実施例１と同様の処理を行い、純度８０．５％のキノリン−８−スルホニルクロライド８．１４ｇを得た。（収率４８％）
(Comparative Example 2)
A reaction vessel equipped with a mechanical stirrer and Dimroth was charged with 48.0 g (0.41 mol) of chlorosulfuric acid and 11.0 g (0.09 mol) of thionyl chloride. Under cooling, 7.8 grams (0.06 mole) of quinoline was charged. While stirring the contents of the flask, the internal temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 10 hours. The reaction solution at this time was analyzed by liquid chromatography. As a result, 62% of quinoline-8-sulfonyl chloride and 10% of quinoline-8-sulfonic acid were produced, and the remaining amount of quinoline as a raw material was 0.1%. It was the following. This reaction solution was treated in the same manner as in Example 1 to obtain 8.14 g of quinoline-8-sulfonyl chloride having a purity of 80.5%. (Yield 48%)
Claims (3)
The reaction temperature of quinoline and chlorosulfuric acid is in the range of 100 to 160 ° C, and the reaction temperature of thionyl chloride is 50 ° C or higher, quinoline-8-sulfonyl according to claim 1-2, A method for producing chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003379986A JP2005139149A (en) | 2003-11-10 | 2003-11-10 | Method for producing quinoline-8-sulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003379986A JP2005139149A (en) | 2003-11-10 | 2003-11-10 | Method for producing quinoline-8-sulfonyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005139149A true JP2005139149A (en) | 2005-06-02 |
Family
ID=34689861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003379986A Pending JP2005139149A (en) | 2003-11-10 | 2003-11-10 | Method for producing quinoline-8-sulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005139149A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422154C (en) * | 2006-04-07 | 2008-10-01 | 北京成宇化工有限公司 | Method for preparing 3-methyl quinolines-8-sulfochlorides |
-
2003
- 2003-11-10 JP JP2003379986A patent/JP2005139149A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422154C (en) * | 2006-04-07 | 2008-10-01 | 北京成宇化工有限公司 | Method for preparing 3-methyl quinolines-8-sulfochlorides |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11180448B2 (en) | Initiator for preparing alkanesulfonic acids from alkane and oleum | |
| KR20190072598A (en) | Solvent-free alkanesulfonation | |
| CN110845502A (en) | Preparation method of 7-bromopyrrolo [2,1-f ] [1,2,4] thiazine-4-amine | |
| JPS6351358A (en) | Production of ditertiary butyl dicarbonate | |
| CN115286514B (en) | Preparation method of 4' -chloro-2-aminobiphenyl sulfate | |
| JP2005139149A (en) | Method for producing quinoline-8-sulfonyl chloride | |
| JP4833419B2 (en) | Production of cyclic acids | |
| CN106748884B (en) | Preparation method of bicalutamide intermediate | |
| JPS6210510B2 (en) | ||
| JP2006193444A (en) | Method for producing 4,4'-dicarboxy-2,2'-bipyridine | |
| CN114736133B (en) | Preparation of 2,4, 5-trifluoro-3-methoxybenzoic acid | |
| JP4913589B2 (en) | One-pot production method of 1,2-benzisoxazole-3-methanesulfonamide | |
| CN113754602B (en) | Synthesis method of 5, 5-dimethyl-4, 5-dihydro-isoxazole-3-one | |
| RU2158257C1 (en) | Method of preparing 4,4'-dichlorodiphenyl sulfoxide | |
| JPH03227974A (en) | Production of quinoline-8-sulfonic acid | |
| JP2003119185A (en) | Method for producing n-methylpiperazinetoluic acid derivative | |
| JPS61134367A (en) | Improved production of phenyl n-(2-biphenilylsulfonyl) carbamate | |
| JP2008247746A (en) | Method for producing haloiodoaniline compounds | |
| JPH03255044A (en) | Preparation of 1,3-bis(2-hydroxyethoxy)benzene | |
| JPH03167153A (en) | Production of 3,5-diiodosalicylic acid | |
| JP2019123673A (en) | Method of producing dichloroquinone derivative | |
| JPH06100477A (en) | Production of iodine compound of fluorene | |
| JP2004075616A (en) | Method for producing 4-halogeno-2-(4-fluorophenylamino)-5,6-dimethylpyrimidine | |
| JP2005112807A (en) | Method for producing aminoalkoxycarbostyryl derivative | |
| TW201827402A (en) | Process for the preparation of 4-alkoxy-3-hydroxypicolinic acids |