JP2942342B2 - Method for producing 1,6-di (Np-chlorophenylbiguanide) hexane - Google Patents
Method for producing 1,6-di (Np-chlorophenylbiguanide) hexaneInfo
- Publication number
- JP2942342B2 JP2942342B2 JP29253290A JP29253290A JP2942342B2 JP 2942342 B2 JP2942342 B2 JP 2942342B2 JP 29253290 A JP29253290 A JP 29253290A JP 29253290 A JP29253290 A JP 29253290A JP 2942342 B2 JP2942342 B2 JP 2942342B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorophenylbiguanide
- hexane
- aqueous solution
- aqueous
- dihydrochloride
- 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 - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は1,6−ジ(N−p−クロロフェニルビグアニ
ド)ヘキサンの製造方法に関する。The present invention relates to a method for producing 1,6-di (Np-chlorophenylbiguanide) hexane.
1,6−ジ(N−p−クロロフェニルビグアニド)ヘキ
サンは、グラム陽性及びグラム陰性のバクテリアに対し
て極めて有効な抗菌剤であり、また防腐剤でもある。1,6-Di (Np-chlorophenylbiguanide) hexane is an extremely effective antibacterial and preservative against Gram-positive and Gram-negative bacteria.
従来、この1,6−ジ(N−p−クロロフェニルビグア
ニド)ヘキサンの製造方法としては、ナトリウムジンア
ナミドとヘキサメチレンジアミン二塩酸塩との縮合等に
よって得られる1,6−ジ(N3−シアノ−N1−グアニジ
ノ)ヘキサンを、p−クロルアニリン塩酸塩と縮合し、
1,6−ジ(N−p−クロロフェニルビグアニド)ヘキサ
ン二塩酸塩とした後、1,6−ジ(N−p−クロロフェニ
ルビグアニド)ヘキサン二塩酸塩の熱水溶液を、過剰な
モル数の水酸化ナトリウムを含有するアルカリ水溶液中
へ加え中和し、析出する固体を別する方法が知られて
いる〔F.L.Rose and G.Swain,L.Chem.Soc,第4422頁〜第
4425頁(1956年)〕。Conventionally, as a method for producing 1,6-di (N-p-chlorophenylbiguanide) hexane, 1,6-di (N 3 − −) obtained by condensation of sodium gin anamide and hexamethylene diamine dihydrochloride or the like is known. Cyano-N 1 -guanidino) hexane is condensed with p-chloroaniline hydrochloride,
After being converted to 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride, a hot aqueous solution of 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride was treated with an excess molar number of hydroxylation. A method of separating a precipitated solid by adding an aqueous solution containing sodium and neutralizing the same is known (FLRose and G. Swain, L. Chem. Soc, pp. 4422 to 442).
4425 (1956)].
しかし、前記ローズらの方法で得られた1,6−ジ(N
−p−クロロフェニルビグアニド)ヘキサンの純度は低
く、さらにメタノール等の溶媒による再結晶を必要とす
るため工業的な製法としては満足できるものではなかっ
た。However, the 1,6-di (N
The purity of (-p-chlorophenylbiguanide) hexane was low, and required recrystallization with a solvent such as methanol, which was not satisfactory as an industrial production method.
したがって、本発明の目的は、従来方法の上記の欠点
を克服し、1,6−ジ(N−p−クロロフェニルビグアニ
ド)ヘキサンを高収率かつ高純度で工業的に製造する方
法を提供するものである。Accordingly, an object of the present invention is to provide a method for industrially producing 1,6-di (Np-chlorophenylbiguanide) hexane with high yield and high purity, which overcomes the above-mentioned disadvantages of the conventional method. It is.
上記目的は本発明によれば、1,6−ジ(N−p−クロ
ロフェニルビグアニド)ヘキサン二塩酸塩を水を含有し
ていてもよい低級アルコールに加えた後、加熱還流下
に、当該二塩酸塩のモル数に対して少なくとも1.8倍モ
ルのアルカリ金属水酸化物又は該アルカリ金属水酸化物
を含有する水溶液を添加中和する1,6−ジ(N−p−ク
ロロフェニルビグアニド)ヘキサンの製造方法により達
成される。According to the present invention, the above object is achieved by adding 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride to a lower alcohol which may contain water, and then heating the mixture under reflux with heating. Process for producing 1,6-di (Np-chlorophenylbiguanide) hexane by adding and neutralizing at least 1.8 moles of an alkali metal hydroxide or an aqueous solution containing the alkali metal hydroxide with respect to the number of moles of a salt Is achieved by
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において用いられる低級アルコールは炭素数1
〜3のアルコールであり、メタノール、エタノールが好
ましく用いられる。アルコール水溶液として用いる場
合、アルコール濃度は特に限定されないが、塩の溶解性
の点からアルコール水溶液中のアルコール濃度は40〜95
重量%、望ましくは50〜80重量%であることが好まし
い。このアルコール濃度が40〜95重量%であるアルコー
ル水溶液を用いる場合には、アルコールそのものを用い
る場合に比して生成物の品質が向上すると共に後処理が
容易となる利点がある。アルコール又はアルコール水溶
液の使用量としては、通常1,6−ジ(N−p−クロロフ
ェニルビグアニド)ヘキサン二塩酸塩の単位重量の好ま
しくは20〜40倍である。40倍を越える溶媒の使用は生成
物の収率を低下させる傾向があり好ましくなく、一方20
倍未満の溶媒量では生成物の品質の低下をまねくことが
あり好ましくない。The lower alcohol used in the present invention has 1 carbon atom.
To 3 alcohols, and methanol and ethanol are preferably used. When used as an aqueous alcohol solution, the alcohol concentration is not particularly limited, but the alcohol concentration in the alcohol aqueous solution is 40 to 95 in view of salt solubility.
%, Desirably 50 to 80% by weight. When an alcohol aqueous solution having an alcohol concentration of 40 to 95% by weight is used, there is an advantage that the quality of the product is improved and the post-treatment is easy as compared with the case where alcohol itself is used. The amount of the alcohol or the aqueous alcohol solution is usually 20 to 40 times the unit weight of 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride. The use of a solvent exceeding 40 times tends to reduce the yield of the product, which is not preferable.
If the amount of the solvent is less than twice, the quality of the product may be deteriorated, which is not preferable.
また中和に使用するアルカリは、アルカリ金属の水酸
化物であり、水酸化カリウム、水酸化ナトリウムが好ま
しく、より好ましくは水酸化ナトリウムである。これら
のアルカリを水に溶解して用いる場合、アルカリ水溶液
中のアルカリ金属水酸化物の濃度は通常3〜15重量%、
好ましくは5〜10重量%である。またアルカリの使用量
は1,6−ジ(N−p−クロロフェニルビグアニド)ヘキ
サン二塩酸塩のモル数に対して、アルカリ水酸化物のモ
ル数で少なくとも1.8倍、好ましくは1.8〜3倍、より好
ましくは1.9〜2.4倍の範囲の量である。1.8倍未満のア
ルカリ量の使用では、生成物の収率の低下や、品質の低
下をもたらし好ましくない。The alkali used for neutralization is an alkali metal hydroxide, preferably potassium hydroxide or sodium hydroxide, more preferably sodium hydroxide. When using these alkalis dissolved in water, the concentration of the alkali metal hydroxide in the aqueous alkali solution is usually 3 to 15% by weight,
Preferably it is 5 to 10% by weight. The amount of the alkali used is at least 1.8 times, preferably 1.8 to 3 times, the number of moles of the alkali hydroxide based on the number of moles of 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride. Preferably, the amount is in the range of 1.9 to 2.4 times. The use of an alkali amount less than 1.8 times is not preferable because it lowers the yield of the product and lowers the quality.
本発明の1,6−ジ(N−p−クロロフェニルビグアニ
ド)ヘキサンは、例えば前記のように1,6−ジ(N3−シ
アノ−N1−グアニジノ)ヘキサンをp−クロルアニリン
塩酸塩と縮合して得られる1,6−ジ(N−p−クロロフ
ェニルビグアニド)ヘキサン二塩酸塩を、前記水を含有
していてもよい低級アルコールに加えた後、加熱還流下
に、前記アルカリ金属水酸化物又はこれを含有する水溶
液を添加・中和することによって製造することができ
る。この場合通常中和反応中の溶液温度は60〜100℃、
好ましくは60〜80℃の範囲に保たれる。中和反応は、溶
液中の固体が完全溶解することを確認して終了するが、
この後加熱を止めて溶液を冷却させ、析出する固体を
別し洗浄溶媒で洗浄、乾燥して1,6−ジ(N−p−クロ
ロフェニルビグアニド)ヘキサンが得られる。洗浄溶媒
としては通常炭素数1〜3のアルコール水溶液が好まし
く用いられ、特に好ましくはメタノール、エタノール水
溶液である。また、洗浄溶媒の量は、生成物の収率向
上、溶媒回収の観点から通常使用する1,6−ジ(N−p
−クロロフェニルビグアニド)ヘキサン二塩酸塩の単位
重量あたり5ml/g〜10ml/g用いられる。1,6 (N-p- chlorophenyl biguanide) hexane of the present invention, for example as the 1,6-(N 3 - cyano -N 1 - guanidino) hexane p- chloroaniline hydrochloride and condensation 1,6-di (N-p-chlorophenylbiguanide) hexane dihydrochloride obtained by the above method is added to the lower alcohol which may contain water, and then the alkali metal hydroxide is heated under reflux. Alternatively, it can be produced by adding and neutralizing an aqueous solution containing the same. In this case, the solution temperature during the neutralization reaction is usually 60 to 100 ° C,
Preferably, it is kept in the range of 60 to 80 ° C. The neutralization reaction is completed after confirming that the solid in the solution is completely dissolved.
Thereafter, the heating is stopped, the solution is cooled, and the precipitated solid is separated, washed with a washing solvent and dried to obtain 1,6-di (Np-chlorophenylbiguanide) hexane. As the washing solvent, an aqueous alcohol solution having usually 1 to 3 carbon atoms is preferably used, and an aqueous methanol or ethanol solution is particularly preferable. Further, the amount of the washing solvent may be adjusted to a value of 1,6-di (N-p
-Chlorophenylbiguanide) used in an amount of 5 ml / g to 10 ml / g per unit weight of hexane dihydrochloride.
次に実施例によって、この発明をさらに具体的に説明
する。Next, the present invention will be described more specifically with reference to examples.
参考例1 1,6−ジ(N3−シアノ−N1−グアニジノ)ヘキサン25
g、p−クロルアニリン塩酸塩35g、およびβ−エトキシ
エタノール250gを混合し、130〜140℃で2時間撹拌し、
冷却後過し、50%酢酸水溶液から再結晶して、融点25
8〜260℃の1,6−ジ(N−p−クロロフェニルビグアニ
ド)ヘキサン二塩酸塩45gを得た。Reference Example 1 1,6-di (N 3 -cyano-N 1 -guanidino) hexane 25
g, 35 g of p-chloroaniline hydrochloride, and 250 g of β-ethoxyethanol, and stirred at 130 to 140 ° C. for 2 hours,
After cooling, the mixture was recrystallized from a 50% aqueous acetic acid solution and had a melting point of 25%.
45 g of 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride at 8-260 ° C. were obtained.
実施例1 1,6−ジ(N−p−クロロフェニルビグアニド)ヘキ
サン二塩酸塩20gを還流冷却器を備えた1の四ツ口フ
ラスコに入れ、65重量%メタノール水溶液700mlに分散
させた。この混合物をバス温100℃にて加熱撹拌し、還
流し始めたところで水酸化ナトリウム2.8gを含む水溶液
34mlを注ぎ、固体が完全溶解したのを確認して加熱を止
め、13℃まで冷却した。その後、析出した固体を別
し、固体を65重量%メタノール水溶液90gで2回洗浄
し、80℃、10mmHgにて乾燥した。非水滴定による純度分
析値99.2%を示す1,6−ジ(N−p−クロロフェニルビ
グアニド)ヘキサン15.2g(収率87%)を得た。(融点1
33〜134℃) 実施例2 還流冷却器を備えた1四ツ口フラスコに、1,6−ジ
(N−p−クロロフェニルビグアニド)ヘキサン二塩酸
塩20gを入れ、65重量%メタノール水溶液700mlに分散さ
せた。この混合液をバス温100℃にて加熱撹拌し、還流
し始めたところで、水酸化ナトリウム3.1gを含む水溶液
76mlを注ぎ、固体が完全に溶解したのを確認して加熱を
止め、12〜13℃まで冷却した。その後析出した固体を65
重量%メタノール水溶液65gで2回洗浄し、80℃、10mmH
gにて乾燥した。純度98%を示す1,6−ジ(N−p−クロ
ロフェニルビグアニド)ヘキサン14.5g(収率83%)を
得た。(融点132.2〜133.2℃) 実施例3 還流冷却器を備えた200ml四ツ口フラスコに、1,6−ジ
(N−p−クロロフェニルビグアニド)ヘキサン二塩酸
塩5g、水酸化ナトリウム1.0g、メタノール50mlを入れ、
バス温80℃にて加熱撹拌した。冷却後、水75mlを注ぎ込
み、固体を別して1,6−ジ(N−p−クロロフェニル
ビグアニド)ヘキサン3.5g(収率80%)を得た。(融点
130〜131.5℃ 純度96%) 比較例1 還流冷却器を備えた四ツ口フラスコに水酸化ナトリウ
ム2.1g及び水50mlを入れ、内温50℃まで加熱した。その
NaOH水溶液に1,6−ジ(N−p−クロロフェニルビグア
ニド)ヘキサン二塩酸塩5.0gの熱水溶液を滴下した。滴
下終了後、反応液を冷却し過後、得られた固体を10mm
Hg、80℃で乾燥し、純度62.8%の1,6−ジ(N−p−ク
ロロフェニルビグアニド)ヘキサン4.26g(収率61.2
%)を得た。Example 1 20 g of 1,6-di (N-p-chlorophenylbiguanide) hexane dihydrochloride was placed in a four-necked flask equipped with a reflux condenser, and dispersed in 700 ml of a 65% by weight aqueous methanol solution. The mixture was heated and stirred at a bath temperature of 100 ° C., and when it began to reflux, an aqueous solution containing 2.8 g of sodium hydroxide
34 ml was poured, and after confirming that the solid was completely dissolved, heating was stopped, and the mixture was cooled to 13 ° C. Thereafter, the precipitated solid was separated, and the solid was washed twice with 90 g of a 65% by weight aqueous methanol solution, and dried at 80 ° C. and 10 mmHg. 15.2 g (87% yield) of 1,6-di (Np-chlorophenylbiguanide) hexane showing a purity analysis value of 99.2% by non-aqueous titration was obtained. (Melting point 1
Example 2 In a four-necked flask equipped with a reflux condenser, 20 g of 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride was placed, and dispersed in 700 ml of a 65% by weight methanol aqueous solution. I let it. This mixture was heated and stirred at a bath temperature of 100 ° C., and when it began to reflux, an aqueous solution containing 3.1 g of sodium hydroxide was used.
76 ml was poured, the heating was stopped when the solid was completely dissolved, and the mixture was cooled to 12 to 13 ° C. Then the precipitated solid is
Wash twice with 65% by weight methanol aqueous solution, 80 ℃, 10mmH
g and dried. 14.5 g (83% yield) of 1,6-di (Np-chlorophenylbiguanide) hexane having a purity of 98% was obtained. Example 3 In a 200 ml four-necked flask equipped with a reflux condenser, 1,6-di (N-p-chlorophenylbiguanide) hexane dihydrochloride 5 g, sodium hydroxide 1.0 g, methanol 50 ml It was placed,
The mixture was heated and stirred at a bath temperature of 80 ° C. After cooling, 75 ml of water was poured, and the solid was separated to obtain 3.5 g of 1,6-di (N-p-chlorophenylbiguanide) hexane (yield 80%). (Melting point
Comparative Example 1 2.1 g of sodium hydroxide and 50 ml of water were placed in a four-necked flask equipped with a reflux condenser and heated to an internal temperature of 50 ° C. That
A hot aqueous solution of 5.0 g of 1,6-di (N-p-chlorophenylbiguanide) hexane dihydrochloride was added dropwise to the aqueous NaOH solution. After the completion of the dropwise addition, the reaction solution was cooled, and the obtained solid was cooled to 10 mm.
Hg, dried at 80 ° C., and 4.26 g of 1,6-di (Np-chlorophenylbiguanide) hexane having a purity of 62.8% (yield: 61.2%).
%).
比較例2 還流冷却器を備えた1四ツ口フラスコに、1,6−ジ
(N−p−クロロフェニルビグアニド)ヘキサン塩酸塩
18gを入れ、65重量%メタノール水溶液630mlに分散させ
た。この混合液をバス温100℃にて加熱撹拌し、還流し
始めたところで水酸化ナトリウム1.6gを含む水溶液20ml
を注ぎ、固体が完全に溶解したのを確認して加熱を止
め、12〜13℃まで冷却した。その後析出した固体を65重
量%メタノール水溶液65gで2回洗浄し、80℃、10mmHg
にて乾燥した。1,6−ジ(N−p−クロロフェニルビグ
アニド)ヘキサン8.0g(収率50.8%)を得た。(融点12
9〜131℃) 〔発明の効果〕 以上述べてきたように、本発明は1,6−ジ(N−p−
クロロフェニルビグアニド)ヘキサン二塩酸塩を水で含
有していてもよい低級アルコールに加えた後、加熱還流
下に、特定量のアルカリ金属水酸化物又は該アルカリ金
属水酸化物を含有する水溶液を添加する方法であるか
ら、1,6−ジ(N−p−クロロフェニルビグアニド)ヘ
キサンを高収率かつ高純度で工業的に製造することがで
き有用である。Comparative Example 2 1,4-di (Np-chlorophenylbiguanide) hexane hydrochloride was placed in a four-necked flask equipped with a reflux condenser.
18 g was added and dispersed in 630 ml of a 65% by weight aqueous methanol solution. This mixture was heated and stirred at a bath temperature of 100 ° C., and when it started to reflux, 20 ml of an aqueous solution containing 1.6 g of sodium hydroxide
And heating was stopped when the solid was completely dissolved, and the mixture was cooled to 12 to 13 ° C. Thereafter, the precipitated solid was washed twice with 65 g of a 65% by weight aqueous methanol solution, and was heated at 80 ° C. and 10 mmHg.
And dried. 8.0 g (yield 50.8%) of 1,6-di (Np-chlorophenylbiguanide) hexane was obtained. (Melting point 12
(Effect of the Invention) As described above, the present invention provides 1,6-di (Np-
(Chlorophenylbiguanide) hexane dihydrochloride is added to a lower alcohol which may contain water, and then a specific amount of an alkali metal hydroxide or an aqueous solution containing the alkali metal hydroxide is added under heating and reflux. Since it is a method, 1,6-di (Np-chlorophenylbiguanide) hexane can be industrially produced in high yield and high purity, and is useful.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C07C 277/08,279/26 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) C07C 277 / 08,279 / 26
Claims (3)
ニド)ヘキサン二塩酸塩を水を含有していてもよい低級
アルコールに加えた後、加熱還流下に、当該二塩酸塩の
モル数に対して少なくとも1.8倍モルのアルカリ金属水
酸化物又は該アルカリ金属水酸化物を含有する水溶液を
添加することを特徴とする1,6−ジ(N−p−クロロフ
ェニルビグアニド)ヘキサンの製造方法。(1) After adding 1,6-di (Np-chlorophenylbiguanide) hexane dihydrochloride to a lower alcohol which may contain water, the mixture is heated to reflux and the number of moles of the dihydrochloride is reduced. 1. A method for producing 1,6-di (Np-chlorophenylbiguanide) hexane, comprising adding at least 1.8 times the molar amount of an alkali metal hydroxide or an aqueous solution containing the alkali metal hydroxide.
が、アルコール濃度40〜95重量%の低級アルコール水溶
液である請求項1記載の製造方法。2. The method according to claim 1, wherein the lower alcohol which may contain water is an aqueous solution of a lower alcohol having an alcohol concentration of 40 to 95% by weight.
用いることを特徴とする請求項1又は2記載の製造方
法。3. The method according to claim 1, wherein 1.8 to 3 moles of the alkali metal hydroxide is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29253290A JP2942342B2 (en) | 1990-10-29 | 1990-10-29 | Method for producing 1,6-di (Np-chlorophenylbiguanide) hexane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29253290A JP2942342B2 (en) | 1990-10-29 | 1990-10-29 | Method for producing 1,6-di (Np-chlorophenylbiguanide) hexane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04164061A JPH04164061A (en) | 1992-06-09 |
JP2942342B2 true JP2942342B2 (en) | 1999-08-30 |
Family
ID=17783020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29253290A Expired - Fee Related JP2942342B2 (en) | 1990-10-29 | 1990-10-29 | Method for producing 1,6-di (Np-chlorophenylbiguanide) hexane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2942342B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008013555A1 (en) * | 2006-07-26 | 2008-01-31 | Watervisions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130065965A1 (en) | 2009-11-18 | 2013-03-14 | Medichem S.A. | Di(4-chloro-phenyldiguanido) derivative which is free of potential genotoxicity and a process for reducing the residual amount of p-chloroaniline in said di(4-chloro-phenyldiguanido) derivative |
-
1990
- 1990-10-29 JP JP29253290A patent/JP2942342B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008013555A1 (en) * | 2006-07-26 | 2008-01-31 | Watervisions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
US7427409B2 (en) | 2006-07-26 | 2008-09-23 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
Also Published As
Publication number | Publication date |
---|---|
JPH04164061A (en) | 1992-06-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
GB2357763B (en) | Process for the preparation of pure citalopram | |
US4767859A (en) | Process for the preparation of pteridine derivatives | |
JP2942342B2 (en) | Method for producing 1,6-di (Np-chlorophenylbiguanide) hexane | |
JPH06271524A (en) | Preparation of aromatic nitrile | |
KR100788529B1 (en) | 3-1-Hydroxy-Pentylidene-5-Nitro-3H-Benzofuran-2-One, a Process for the Preparation thereof and the Use thereof | |
JP4097291B2 (en) | Method for producing substituted valinamide derivative | |
HU225298B1 (en) | Novel process for the preparation of alpha-(2,4-disulfophenyl)-n-tert-butylnitrone and pharmaceutically acceptable salts thereof | |
JP3031279B2 (en) | Method for producing 2-alkoxy-6- (trifluoromethyl) pyrimidin-4-ol | |
US4145548A (en) | Method for the production of 5-nitroso-2,4,6-triaminopyrimidine | |
JP4700777B2 (en) | Improved process for the preparation of 4-amino-1,2,4-triazolin-5-one | |
HERBST et al. | Synthesis of Iminotetrazoline Derivatives as Trichomonacidal and Fungicidal Agents1, 2 | |
JP4790901B2 (en) | Process for producing 4-amino-5-cyanoimidazole derivative and its intermediate | |
JPH0597782A (en) | Production of bevantolol hydrochloride | |
JPH0573738B2 (en) | ||
JP4342645B2 (en) | Method for producing imidazoline compound | |
JP2813008B2 (en) | Method for producing pyrazinamines | |
JP2002155058A (en) | Method for producing 1-substituted hydratoin compound | |
JP4260296B2 (en) | Method for producing amidoamine compound | |
JP3176261B2 (en) | Method for producing anthraquinone compound | |
US4248891A (en) | 1-(1-Aminoalkyl)tricyclo[4,3,1,12,5 ]undecanes | |
JP4375943B2 (en) | Method for producing powder N-long chain acylimino dibasic acid salt | |
JPH0725539B2 (en) | Method for producing dicyanamide metal salt | |
JP4739695B2 (en) | Process for producing 5-amino-1-substituted-1,2,4-triazole, and triazole derivative obtained by the process | |
US4229375A (en) | 1-Aminomethyltricyclo[4.3.1.12,5 ]undecane and acid-addition salts thereof | |
JP2911296B2 (en) | Method for producing tris (4-hydroxybenzyl) isocyanurate compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |