JPS6156230B2 - - Google Patents
Info
- Publication number
- JPS6156230B2 JPS6156230B2 JP6365578A JP6365578A JPS6156230B2 JP S6156230 B2 JPS6156230 B2 JP S6156230B2 JP 6365578 A JP6365578 A JP 6365578A JP 6365578 A JP6365578 A JP 6365578A JP S6156230 B2 JPS6156230 B2 JP S6156230B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- crystals
- acid
- producing
- product
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- -1 dicyanopyrazine compound Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 2
- HYELGFFHLBUUOH-UHFFFAOYSA-N 3-cyanopyrazine-2-carboxamide Chemical compound NC(=O)C1=NC=CN=C1C#N HYELGFFHLBUUOH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- VPRRXMCIOHZBCX-UHFFFAOYSA-N 5,6-dimethylpyrazine-2,3-dicarbonitrile Chemical compound CC1=NC(C#N)=C(C#N)N=C1C VPRRXMCIOHZBCX-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OTVZGAXESBAAQQ-UHFFFAOYSA-N pyrazine-2,3-dicarbonitrile Chemical compound N#CC1=NC=CN=C1C#N OTVZGAXESBAAQQ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は、ピラジンシアノカルボキシアミド化
合物の製造方法に関する。更に詳しくは、一般式
（）
（式中Ｒは水素原子、アルキル基又はフエニル基
を示す）
で、表わされる、ジシアノピラジン化合物（以下
「化合物」と略記する。）を塩酸と酢酸の混合酸
中で、反応させ、一般式（）
で表わされる、ピラジンシアノカルボキシアミド
化合物（但し式（）中Ｒは、前記載と同じ意味
を有する。以下「化合物」と略記する。）を製
造する方法に関するものであり、その目的は化合
物から化合物を、好収率で、容易に得る方法
を提供することにある。化合物は、医薬、農
薬、染顔料等の中間体特に、顔料製造の中間体と
して重要な化合物である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a pyrazine cyanocarboxamide compound. For more details, see the general formula () (In the formula, R represents a hydrogen atom, an alkyl group, or a phenyl group.) A dicyanopyrazine compound (hereinafter abbreviated as "compound") represented by the following is reacted in a mixed acid of hydrochloric acid and acetic acid, and the general formula ( ) This article relates to a method for producing a pyrazine cyanocarboxamide compound (wherein R in formula () has the same meaning as described above. Hereinafter abbreviated as "compound") represented by The object of the present invention is to provide a method for easily obtaining the following in good yield. The compound is an important compound as an intermediate for medicines, agricultural chemicals, dyes and pigments, and especially as an intermediate for pigment production.
従来化合物から化合物を製造する方法とし
て、例えば２・３−ジアノピラジンを原料として
２−シアノピラジン−３−カルボキシアミドを製
造する方法としては、アルコール溶液中でモリブ
デン酸ナトリウムを触媒して過酸化水素と反応さ
せることが知られている。本発明は、このような
従来法に比べて容易に化合物から化合物を製
造する方法として、酸を用いた加水分解により、
シアノ基の１つを選択的にカルボキシアミド基に
転換させることについて検討を重ねた結果完成さ
れたものである。 As a conventional method for producing a compound from a compound, for example, a method for producing 2-cyanopyrazine-3-carboxamide using 2,3-dianopyrazine as a raw material is to catalyze sodium molybdate in an alcohol solution to form hydrogen peroxide. It is known to cause a reaction. The present invention provides a method for producing a compound from a compound more easily than such conventional methods by hydrolysis using an acid.
This was completed as a result of repeated studies on selectively converting one of the cyano groups to a carboxamide group.
本発明は、化合物を塩酸と酢酸の混合酸で処
理することを特徴とする化合物の製造方法であ
る。 The present invention is a method for producing a compound, which is characterized by treating the compound with a mixed acid of hydrochloric acid and acetic acid.
本発明の原料である化合物はジアミノマレオ
ニトリル（DAMN）にα−ジケトン類を反応さ
せて得られるもので、
におけるＲはＨ又はアルキル基もしくはフエニル
基を示すものであり、これらは置換基を含むもの
であつてもよい。 The compound that is the raw material of the present invention is obtained by reacting diaminomaleonitrile (DAMN) with α-diketones. R represents H, an alkyl group, or a phenyl group, and these may contain a substituent.
本発明に係る塩酸と酢酸の混合酸としては、化
合物に対して、約20重量％以上の塩酸を３〜20
重量倍好ましくは５〜10重量倍と、0.5〜40重量
倍好ましくは１〜30重量倍の酢酸とを混合したも
のが好適に使用される。 As the mixed acid of hydrochloric acid and acetic acid according to the present invention, about 20% by weight or more of hydrochloric acid is added at 3 to 20% by weight based on the compound.
A mixture of 5 to 10 times by weight, preferably 5 to 10 times by weight, and 0.5 to 40 times by weight, preferably 1 to 30 times by weight of acetic acid is preferably used.
本発明の方法の実施に当つては、目的とする化
合物の生成の他に、逐次反応の結果として
が副生することがあるので、反応温度（通常室温
〜80℃）、反応時間（通常30分〜20時間）を、混
合酸の組成と組合せた反応条件を選定することが
望ましい。 In carrying out the method of the present invention, in addition to producing the target compound, as a result of the sequential reactions, may be produced as a by-product, it is desirable to select reaction conditions that combine the reaction temperature (usually room temperature to 80°C) and reaction time (usually 30 minutes to 20 hours) with the composition of the mixed acid.
反応が終了したら、反応生成液を冷却して晶柝
する結晶を濾取するか、あるいは結晶の晶柝が生
じない場合は、反応液を、水中へ投入し、柝出す
る生成物を濾取する。未反応原料及び副生物を除
去するためには、例えばアセトン、メタノール、
エタノール、クロロホルム等の溶剤で洗浄すれば
よい。 After the reaction is completed, the reaction product solution is cooled and the crystals to be crystallized are collected by filtration, or if no crystals are formed, the reaction solution is poured into water and the precipitated product is collected by filtration. do. In order to remove unreacted raw materials and by-products, for example, acetone, methanol,
It may be washed with a solvent such as ethanol or chloroform.
このように、本発明によれば、極めて容易な方
法で、約60〜90％の収率で化合物から化合物
を製造することが可能になる。 Thus, according to the present invention, it becomes possible to produce a compound from a compound in a very easy manner with a yield of about 60 to 90%.
以下に実施例をあげて、本発明を更に説明す
る。 The present invention will be further explained with reference to Examples below.
実施例 １
100mlの４頚のフラスコに、２・３−ジアノピ
ラジン5.0ｇ、35％塩酸40ml、酢酸５mlを同時に
仕込み、30〜35℃でで３時間15分撹拌保持した。
反応液を０〜５℃に冷却し晶柝した結晶を濾取し
た。この結晶をアセトン10mlを用いて洗浄して90
〜100℃で８時間乾燥して、生成物4.9ｇを得た。
この生成物は白色針状物で、mp270〜273℃を示
し２−シアノピラジン−３−カルボキシアミドの
標品とIR、元素分柝値、質量分柝値、NMRが完
全に一致した。収率86.1％。Example 1 5.0 g of 2,3-dianopyrazine, 40 ml of 35% hydrochloric acid, and 5 ml of acetic acid were charged simultaneously into a 100 ml four-necked flask, and the mixture was stirred and held at 30 to 35°C for 3 hours and 15 minutes.
The reaction solution was cooled to 0 to 5°C, and the crystals were collected by filtration. Wash the crystals with 10 ml of acetone and
Drying at ˜100° C. for 8 hours yielded 4.9 g of product.
This product was a white needle-like substance with an mp of 270 to 273°C, and its IR, elemental content, mass content, and NMR completely matched those of the standard 2-cyanopyrazine-3-carboxamide. Yield 86.1%.
実施例 ２
実施例１と同様な仕込みを行ない、28〜32℃で
３時間撹拌保持した。反応液を氷水200ml中へ投
入し、０〜５℃で一昼夜放置后晶柝した結晶を濾
取し、アセトン10mlで洗浄后、実施例１と同様に
処理して、２−シアノピラジン−３−カルボキシ
アミド5.12ｇを得た。収率90％。Example 2 The same preparation as in Example 1 was carried out, and the mixture was stirred and maintained at 28 to 32°C for 3 hours. The reaction solution was poured into 200 ml of ice water and allowed to stand overnight at 0 to 5°C. The crystals were collected by filtration, washed with 10 ml of acetone, and treated in the same manner as in Example 1 to obtain 2-cyanopyrazine-3-. 5.12 g of carboxamide was obtained. Yield 90%.
実施例 ３
100ml４頚フラスコに、５・６−ジメチル−
２・３−ジシアノピラジン5.0ｇ、35％塩酸30ml
を同時に仕込み40〜45℃で、３時間15分撹拌保持
した。反応液を250mlの氷水中へ投入し、一昼夜
０〜５℃で放置后、晶柝した結晶を濾取した。こ
の結晶を０〜５℃に冷却したエタノール15mlで洗
浄后、実施例１と同様に乾燥して、淡茶白色、針
状結晶の生成物4.15ｇを得た。この生成物は
mp210〜211℃を示し、５・６−ジメチルピラジ
ン−２−シアノ−３−カルボキシアミドの標品と
IR、元素分柝値、質量分柝値、NMRが完全に一
致した。収率74.5％。Example 3 In a 100ml four-necked flask, add 5,6-dimethyl-
2,3-dicyanopyrazine 5.0g, 35% hydrochloric acid 30ml
were charged at the same time and kept stirring at 40 to 45°C for 3 hours and 15 minutes. The reaction solution was poured into 250 ml of ice water and allowed to stand at 0 to 5°C overnight, and then the crystals were collected by filtration. The crystals were washed with 15 ml of ethanol cooled to 0 to 5°C, and then dried in the same manner as in Example 1 to obtain 4.15 g of a light brown-white, needle-shaped crystal product. This product is
mp210-211℃, and it is different from the standard of 5,6-dimethylpyrazine-2-cyano-3-carboxamide.
IR, elemental content, mass content, and NMR were in perfect agreement. Yield 74.5%.
実施例 ４
100ml４頚のフラスコに５・６−ジフエニル−
２・３−ジシアノピラジン3.0ｇ、35％塩酸20
ml、酢酸70mlを同時に仕込み、60〜65℃で、４時
間撹拌保持した。反応液を300mlの氷水中へ投入
し、一昼夜放置后、晶柝した結晶を濾取した。こ
の結晶をクロロホルム50mlで良く洗浄ののち、乾
燥して白色粉末生成物1.93ｇを得た。この生成物
はmp240〜242℃（分解）を示し、５・６−ジフ
エニルピラジン−２−シアノ−３−カルボキシア
ミドの標品とIR、元素分柝値、質量分柝値、
NMRが完全に一致した。収率60.5％。Example 4 5,6-diphenyl in a 100ml 4-necked flask
2,3-dicyanopyrazine 3.0g, 35% hydrochloric acid 20
ml and 70 ml of acetic acid were charged at the same time, and the mixture was stirred and maintained at 60 to 65°C for 4 hours. The reaction solution was poured into 300 ml of ice water, and after being left overnight, the crystals were collected by filtration. The crystals were thoroughly washed with 50 ml of chloroform and then dried to obtain 1.93 g of a white powder product. This product showed an mp of 240 to 242°C (decomposition), and compared with the standard of 5,6-diphenylpyrazine-2-cyano-3-carboxamide, IR, elemental content value, mass content value,
NMR matched perfectly. Yield 60.5%.
Claims (1)
中、Ｒは水素原子、アルキル基又はフエニル基を
示す。）を塩酸と酢酸の混合酸中で反応させるこ
とを特徴とする、一般式 で表わされる、ピラジンシアノカルボキシアミド
化合物（但し、式中Ｒは前記と同じ。）の製造方
法。[Claims] 1. General formula A dicyanopyrazine compound represented by (wherein R represents a hydrogen atom, an alkyl group, or a phenyl group) is reacted in a mixed acid of hydrochloric acid and acetic acid, A method for producing a pyrazine cyanocarboxamide compound represented by (wherein R is the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6365578A JPS54154776A (en) | 1978-05-27 | 1978-05-27 | Preparation of cyano-pyrazinecarboxamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6365578A JPS54154776A (en) | 1978-05-27 | 1978-05-27 | Preparation of cyano-pyrazinecarboxamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54154776A JPS54154776A (en) | 1979-12-06 |
| JPS6156230B2 true JPS6156230B2 (en) | 1986-12-01 |
Family
ID=13235570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6365578A Granted JPS54154776A (en) | 1978-05-27 | 1978-05-27 | Preparation of cyano-pyrazinecarboxamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54154776A (en) |
-
1978
- 1978-05-27 JP JP6365578A patent/JPS54154776A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54154776A (en) | 1979-12-06 |
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