JPH072726B2 - Method for producing benzoguanamine derivative - Google Patents
Method for producing benzoguanamine derivativeInfo
- Publication number
- JPH072726B2 JPH072726B2 JP61135196A JP13519686A JPH072726B2 JP H072726 B2 JPH072726 B2 JP H072726B2 JP 61135196 A JP61135196 A JP 61135196A JP 13519686 A JP13519686 A JP 13519686A JP H072726 B2 JPH072726 B2 JP H072726B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- present
- dichlorobenzonitrile
- compound
- iii
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 title claims description 3
- LNGWRTKJZCBXGT-UHFFFAOYSA-N 2,5-dichlorobenzonitrile Chemical compound ClC1=CC=C(Cl)C(C#N)=C1 LNGWRTKJZCBXGT-UHFFFAOYSA-N 0.000 claims description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000007810 chemical reaction solvent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000767 anti-ulcer Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 1
- -1 2,5-dichlorophenyl Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003699 antiulcer agent Substances 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は次の式〔III〕 で表わされるベンゾグアナミン誘導体の製造法に関す
る。本発明に係る化合物〔III〕は抗潰瘍作用を示し抗
潰瘍剤として有用であるほか、〔III〕のマレイン酸塩
はこれまでにない顕著な抗潰瘍作用を有することが判明
しており、医薬品の合成中間体としても有用な化合物で
ある。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides the following formula [III]: And a method for producing a benzoguanamine derivative represented by The compound [III] according to the present invention shows an anti-ulcer activity and is useful as an anti-ulcer agent, and the maleic acid salt of [III] has been found to have an unprecedented remarkable anti-ulcer activity. It is also a useful compound as a synthetic intermediate.
（従来の技術） ベンゾグアナミンタイプの化合物は、ベンゾニトリル類
とジシアンジアミドとを高沸点アルコール中でアルカリ
触媒の存在下に反応させて取得するのがこれまでの一般
的な方法であった（Org.Syn.coll.vol.IV.78等）。(Prior Art) A benzoguanamine-type compound was obtained by reacting benzonitriles with dicyandiamide in a high-boiling-point alcohol in the presence of an alkali catalyst (Org.Syn). .coll.vol.IV.78 etc.).
式〔III〕で表わされる化合物は、本出願の出願人によ
って出願された一連の特許によってその顕著な薬理作用
とともに新規化合物として見いだされたもので、例えば
特公昭55−4751号公報（特許第1017236号）には、2,5−
ジクロルベンゾニトリルとジシアンジアミドとをメチル
セロソルブに溶解して水酸化カリウムの存在下に反応さ
せると式〔III〕で表わされる化合物を取得することが
できることが具体的実施例をもって記載されている。The compound represented by the formula [III] was found as a novel compound with its remarkable pharmacological action by a series of patents filed by the applicant of the present application. For example, JP-B-55-4751 (Patent No. 1017236). No.), 2,5-
It is described in specific examples that the compound represented by the formula [III] can be obtained by dissolving dichlorobenzonitrile and dicyandiamide in methyl cellosolve and reacting them in the presence of potassium hydroxide.
（発明が解決しようとする問題点） 本発明者らは式〔III〕で表わされる化合物の重要な医
薬的効果に着目して式〔III〕化合物の更に有利な製法
を鋭意研究してきたところであったが、その過程で、上
記方法によって取得された式〔III〕化合物には、極微
量ではあるが副生物が生じることを見いだした。上記製
法による場合、この副生物は生成物に対して２〜４％の
割合で混在することが確認された。医薬品とする場合、
化合物は純粋な単一物として薬理効果、毒性等を検定す
ることが必須であるから、たとえ２〜３％であっても混
在する副生物を除去することが必要であると考えられる
ところ、これらを除去するためには数度、十数度の精製
過程が必要であり、これらの操作の過程で大幅な収量低
下が生じる結果となることも判った。(Problems to be Solved by the Invention) The present inventors have been earnestly researching a more advantageous production method of the compound of the formula [III] by paying attention to the important medicinal effect of the compound of the formula [III]. However, in the process, it was found that the compound of the formula [III] obtained by the above-mentioned method produced a by-product although the amount was extremely small. According to the above-mentioned production method, it was confirmed that this by-product was mixed in a ratio of 2 to 4% with respect to the product. When using as a medicine
Since it is essential to test the pharmacological effect, toxicity, etc. of a compound as a pure single substance, it is considered necessary to remove coexisting by-products even if it is 2 to 3%. It was also found that a purification process of several times and a dozen or more times is required to remove the above-mentioned substances, resulting in a large decrease in yield in the process of these operations.
そこで、この副生物を単離してその構造を解析してみた
結果、このものが原料である2,5−ジクロルベンゾニト
リルと溶媒であるメチルセルソルブとが反応した結果生
じた化合物〔IV〕であることを見いだした。更に反応溶
媒としてシクロヘキサノールをメチルセロソルブの代わ
りに使用して同様の反応を試みたところ、化合物〔Ｖ〕
を副生することも判った。Therefore, as a result of isolating this by-product and analyzing its structure, a compound formed as a result of the reaction of 2,5-dichlorobenzonitrile as a raw material with methylcellosolve as a solvent [IV] I found that. Furthermore, when a similar reaction was tried using cyclohexanol as a reaction solvent instead of methyl cellosolve, the compound [V]
Was also found to be a by-product.
そこで、本発明者らは2,5−ジクロルベンゾニトリルの
２位のクロル基が反応溶媒であるアルコールとは置換反
応を起こさない手段の確立を目指して、更には目的物た
る〔III〕の最終的な収量の向上を目指して研究を続行
することとなった。 Then, the inventors of the present invention aim to establish means for preventing the substitution reaction of the chloro group at the 2-position of 2,5-dichlorobenzonitrile with the alcohol which is the reaction solvent. It was decided to continue the study aiming at the final improvement in yield.
従って、本発明の目的は以下の点にあった。Therefore, the objects of the present invention are as follows.
2,5−ジクロルベンゾニトリルとジシアンジアミドと
の反応にあたって、目的物たる式〔III〕化合物以外の
副生物を生じることがないこと。In the reaction of 2,5-dichlorobenzonitrile with dicyandiamide, no by-products other than the desired compound of formula [III] should be produced.
その反応がこれまで以上に収率の高いものであるこ
と。The reaction has a higher yield than ever before.
（問題点を解決するための手段） 本発明者らは上記目的のために鋭意研究の結果、僥倖で
はあったが極めて単純な工夫によって上記問題点が解決
することを見いだし、本発明を完成させることに成功し
た。(Means for Solving Problems) As a result of intensive research for the above purpose, the present inventors have found that the above problems can be solved by an extremely simple device although it is a definite result, and the present invention is completed. Was successful.
本発明の要旨は、2,5−ジクロルベンゾニトリルとジシ
アンジアミドとの反応において、反応溶媒として第三級
アルコールを用いることにある。The gist of the present invention is to use a tertiary alcohol as a reaction solvent in the reaction between 2,5-dichlorobenzonitrile and dicyandiamide.
本発明に用いられる第三級アルコールとしては、例え
ば、tert−ブチルアルコール、tert−アミルアルコール
等を挙げることができる。Examples of the tertiary alcohol used in the present invention include tert-butyl alcohol and tert-amyl alcohol.
本発明に用いられる第三級アルコールの反応溶媒として
の量は反応条件により一概に限定することができない
が、好ましくは、原料である2,5−ジクロルベンゾニト
リルに対して10倍量（v/w）以上用いるのが良い。The amount of the tertiary alcohol used in the present invention as a reaction solvent cannot be unconditionally limited depending on the reaction conditions, but it is preferably 10 times the amount of 2,5-dichlorobenzonitrile as a raw material (v / w) It is better to use more than.
本発明は、上述した既知の方法におけるメチルセロソル
ブの代わりに第三級アルコールを用いるものである。本
発明におけるアルカリ触媒の量は、従って既知の方法と
同様のものでよく、反応条件により一概に限定すること
ができないが、好ましくは2,5−ジクロルベンゾニトリ
ルに対して４〜20％モルを用いるのがよい。また、本発
明の反応条件は特に限定的なものではないが、好ましく
は反応温度は80℃前後、反応時間は８〜12時間程度で充
分である。The present invention uses a tertiary alcohol in place of methyl cellosolve in the known method described above. The amount of the alkali catalyst in the present invention may be the same as in the known method, and cannot be unconditionally limited depending on the reaction conditions, but it is preferably 4 to 20% mol based on 2,5-dichlorobenzonitrile. It is better to use. The reaction conditions of the present invention are not particularly limited, but a reaction temperature of about 80 ° C. and a reaction time of about 8 to 12 hours are preferable.
（作用） 本発明の効果がいかなる操作によって生じるかは定かで
はないが、一般に第三級アルコールはそのアルコール基
に直接に接する複数の炭素によって立体障害が生じ、原
料たる2,5−ジクロベンゾニトリルの２位のクロルとの
反応が生じにくくなるのかも知れない。(Operation) Although it is not known by what operation the effect of the present invention is caused, generally, a tertiary alcohol is sterically hindered by a plurality of carbons which are in direct contact with the alcohol group, and the starting material 2,5-dichlorobenzonitrile is generated. It may be difficult for the reaction with the 2nd-position chlorine to occur.
（発明の効果） これまでのメチルセロソルブを反応溶媒として用いる方
法では、その反応収率は85〜86％であるに過ぎなかった
が、本発明の方法によれば94〜95％の収率を挙げること
ができた。(Effect of the Invention) In the method using methyl cellosolve as a reaction solvent up to now, the reaction yield was only 85 to 86%, but according to the method of the present invention, a yield of 94 to 95% was obtained. I was able to name it.
また、これまでのメチルセロソルブを反応溶媒として用
いる方法では、反応終了時に目的物以外２〜４％の副生
物を生じていたが、本発明の方法によれば、副生物は全
く生じることがなかった。Further, in the conventional method using methyl cellosolve as a reaction solvent, 2 to 4% of a by-product other than the target product was produced at the end of the reaction, but according to the method of the present invention, the by-product is not produced at all. It was
これらの事実は、本発明の方法が純良医薬品を提供する
場合に極めて有用であることを示すものである。These facts show that the method of the present invention is extremely useful in providing a pure drug.
（実施例） 以下に本発明の実施例を掲げて本発明を更に詳しく説明
する。(Example) Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention.
実施例１ 100ml四径コルベンに攪拌装置、温度計及びストッパー
をセットし、2,5−ジクロルベンゾニトリルを5g（0.002
91mol）、ジシアンジアミド35g（0.0416mol）を入れ、t
ert−ブタノール50mlを入れて攪拌を開始し、反応温度
を80℃に保つ。水酸化カリウム120mg（0.0021mol）を添
加し、反応温度を80℃に保ちながら10時間反応を行う。
反応終了後、一晩冷却放置し、翌日、晶出した白色結晶
を濾取し、tert−ブタノール、温水及びトルエルで洗浄
し、乾燥すると目的物たる式〔III〕で表わされる化合
物2,4−ジアミノ−６−（2,5−ジクロロフェニル）−ｓ
−トリアジンが7.08g得られた（収率95％）。Example 1 A stirring device, a thermometer and a stopper were set in a 100 ml four-diameter Kolben, and 5 g (0.002) of 2,5-dichlorobenzonitrile was added.
91mol), dicyandiamide 35g (0.0416mol), t
Add 50 ml of ert-butanol and start stirring to keep the reaction temperature at 80 ° C. 120 mg (0.0021 mol) of potassium hydroxide is added, and the reaction is carried out for 10 hours while maintaining the reaction temperature at 80 ° C.
After completion of the reaction, the mixture was left to cool overnight, and the next day, the white crystals that crystallized were collected by filtration, washed with tert-butanol, warm water and toluel, and dried to obtain the desired compound of the formula [III] 2,4- Diamino-6- (2,5-dichlorophenyl) -s
-7.08 g of triazine was obtained (95% yield).
最終取得物を下記に示す分析条件で分析したところ、不
純物は全く副生していないことが判明した。When the final product was analyzed under the analysis conditions shown below, it was found that no impurities were by-produced.
〈高速液体クロマトグラフィー分析条件〉 カラム:Nucleosil 5C18 4mm×25cm 移動相：アセトニトリル：水：氷酢酸 85:300:1.2 1.0ml/min カラム温度:25℃ 検出波長:230nm 同様にして、以下の結果を得た。<High-performance liquid chromatography analysis conditions> Column: Nucleosil 5C 18 4 mm × 25 cm Mobile phase: Acetonitrile: Water: Glacial acetic acid 85: 300: 1.2 1.0 ml / min Column temperature: 25 ° C Detection wavelength: 230 nm Similarly, the following results were obtained. Got
実施例２ 2,5−ジクロルベンゾニトリル 5g（0.0291mol） ジシアンジアミド 35g（0.0416mol） 水酸化カリウム 120mg（0.0021mol） 反応溶媒:tert−アミルアルコール 50ml 反応温度:80℃ 反応時間:10時間 収量:7g（94％） 分析結果：高速液体クロマトグラフィー分析を行ったと
ころ、不純物は生成していないことが判った。Example 2 2,5-Dichlorobenzonitrile 5 g (0.0291 mol) Dicyandiamide 35 g (0.0416 mol) Potassium hydroxide 120 mg (0.0021 mol) Reaction solvent: tert-amyl alcohol 50 ml Reaction temperature: 80 ° C. Reaction time: 10 hours Yield: 7 g (94%) Analytical results: High performance liquid chromatography analysis revealed that no impurities were produced.
参考例１ 2,5−ジクロルベンゾニトリル 5g（0.0291mol） ジシアンジアミド 35g（0.0416mol） 水酸化カリウム 120mg（0.0021mol） 反応溶媒：メチルセロソルブ 50ml 反応温度:80℃ 反応時間:10時間 収量:6.3g（85％） 分析結果：高速液体クロマトグラフィー分析を行ったと
ころ、不純物〔IV〕を面積百分率で2.6％生成している
ことを確認した。Reference Example 1 2,5-Dichlorobenzonitrile 5g (0.0291mol) Dicyandiamide 35g (0.0416mol) Potassium hydroxide 120mg (0.0021mol) Reaction solvent: Methylcellosolve 50ml Reaction temperature: 80 ° C Reaction time: 10 hours Yield: 6.3g (85%) Analysis results: High performance liquid chromatography analysis confirmed that impurities [IV] were produced in an area percentage of 2.6%.
参考例２ 2,5−ジクロルベンゾニトリル 5g（0.0291mol） ジシアンジアミド 35g（0.0416mol） 水酸化カリウム 120mg（0.0021mol） 反応溶媒：シクロヘキサノール 50ml 反応温度:80℃ 反応時間:10時間 収量:6.18g（83％） 分析結果：高速液体クロマトグラフィー分析を行ったと
ころ、不純物〔Ｖ〕を面積百分率で3.8％生成している
ことを確認した。Reference Example 2 2,5-Dichlorobenzonitrile 5g (0.0291mol) Dicyandiamide 35g (0.0416mol) Potassium hydroxide 120mg (0.0021mol) Reaction solvent: Cyclohexanol 50ml Reaction temperature: 80 ° C Reaction time: 10 hours Yield: 6.18g (83%) Analysis result: High performance liquid chromatography analysis confirmed that impurity [V] was produced in an area percentage of 3.8%.
Claims (1)
ジアミドを第三級アルコール中でアルカリ触媒存在下に
反応させることを特徴とする、次の式〔III〕 で表わされるベンゾグアナミン誘導体の製造法。1. The following formula [III] characterized in that 2,5-dichlorobenzonitrile and dicyandiamide are reacted in a tertiary alcohol in the presence of an alkali catalyst. A method for producing a benzoguanamine derivative represented by:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61135196A JPH072726B2 (en) | 1986-06-10 | 1986-06-10 | Method for producing benzoguanamine derivative |
| CA000538701A CA1290754C (en) | 1986-06-10 | 1987-06-03 | Method of manufacturing benzoguanamine derivatives |
| ES8701678A ES2005249A6 (en) | 1986-06-10 | 1987-06-08 | Production of benzoguanamine derivative |
| AT0144887A AT395713B (en) | 1986-06-10 | 1987-06-09 | METHOD FOR PRODUCING 2,4-DIAMINO-6- (2,5-DICHLORPHENYL) -S-TRIAZINE |
| KR1019870005855A KR950005204B1 (en) | 1986-06-10 | 1987-06-10 | Preparation of benzoguanamine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61135196A JPH072726B2 (en) | 1986-06-10 | 1986-06-10 | Method for producing benzoguanamine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62292771A JPS62292771A (en) | 1987-12-19 |
| JPH072726B2 true JPH072726B2 (en) | 1995-01-18 |
Family
ID=15146092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61135196A Expired - Lifetime JPH072726B2 (en) | 1986-06-10 | 1986-06-10 | Method for producing benzoguanamine derivative |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH072726B2 (en) |
| KR (1) | KR950005204B1 (en) |
| AT (1) | AT395713B (en) |
| CA (1) | CA1290754C (en) |
| ES (1) | ES2005249A6 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6150362A (en) * | 1997-12-12 | 2000-11-21 | Henkin; Jack | Triazine angiogenesis inhibitors |
| KR101289575B1 (en) * | 2012-09-07 | 2013-07-24 | 박충만 | The roast chicken manufacture method |
| CN106187928B (en) * | 2016-08-02 | 2019-06-07 | 安徽省逸欣铭医药科技有限公司 | A kind of preparation method of irsogladine maleate |
| KR101896105B1 (en) * | 2017-08-28 | 2018-09-07 | 최용선 | Process for preparing Food formulation with rolled type |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1441904A (en) * | 1974-02-18 | 1976-07-07 | Nippon Shinyaku Co Ltd | Benzoguanamine derivatives |
| JPS5925765B2 (en) * | 1981-08-04 | 1984-06-21 | 日本新薬株式会社 | Peptic ulcer treatment agent |
-
1986
- 1986-06-10 JP JP61135196A patent/JPH072726B2/en not_active Expired - Lifetime
-
1987
- 1987-06-03 CA CA000538701A patent/CA1290754C/en not_active Expired - Lifetime
- 1987-06-08 ES ES8701678A patent/ES2005249A6/en not_active Expired
- 1987-06-09 AT AT0144887A patent/AT395713B/en not_active IP Right Cessation
- 1987-06-10 KR KR1019870005855A patent/KR950005204B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATA144887A (en) | 1992-07-15 |
| JPS62292771A (en) | 1987-12-19 |
| ES2005249A6 (en) | 1989-03-01 |
| KR880000411A (en) | 1988-03-25 |
| CA1290754C (en) | 1991-10-15 |
| KR950005204B1 (en) | 1995-05-19 |
| AT395713B (en) | 1993-02-25 |
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