JP2003292478A - 3-hydrazono-2-hydroxyiminopropionitrile derivative and method for producing the same - Google Patents
3-hydrazono-2-hydroxyiminopropionitrile derivative and method for producing the sameInfo
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- JP2003292478A JP2003292478A JP2002101259A JP2002101259A JP2003292478A JP 2003292478 A JP2003292478 A JP 2003292478A JP 2002101259 A JP2002101259 A JP 2002101259A JP 2002101259 A JP2002101259 A JP 2002101259A JP 2003292478 A JP2003292478 A JP 2003292478A
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- Prior art keywords
- hydroxyiminopropionitrile
- hydrazono
- derivative
- group
- producing
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、医薬・農薬等の合
成中間体として有用な、新規な3-ヒドラゾノ-2-ヒドロ
キシイミノプロピオニトリル誘導体及びその製法に関す
る。TECHNICAL FIELD The present invention relates to a novel 3-hydrazono-2-hydroxyiminopropionitrile derivative useful as a synthetic intermediate for pharmaceuticals, agricultural chemicals and the like, and a process for producing the same.
【０００２】[0002]
【従来の技術】従来、3-ヒドラゾノ-2-ヒドロキシイミ
ノプロピオニトリル誘導体に係る技術としては、Khim.G
eterotsikl.Soedin.,7,976(1991)に、3-(β-ジメチルヒ
ドラゾノ-α-オキシイミノエチル)-1,2,4-オキサジアゾ
−ルから、3-(ジメチルヒドラゾノ)-2-ヒドロキシイミ
ノプロピオニトリルを製造する方法が記載されているの
みであり、本発明の3-ヒドラゾノ-2-ヒドロキシイミノ
プロピオニトリル誘導体は、新規な化合物であり、従来
までにその製法は全く知られていなかった。2. Description of the Related Art Conventionally, as a technology relating to a 3-hydrazono-2-hydroxyiminopropionitrile derivative, Khim.
eterotsikl.Soedin., 7 , 976 (1991), 3- (β-dimethylhydrazono-α-oxyiminoethyl) -1,2,4-oxadiazol, 3- (dimethylhydrazono) -2- Only the method for producing hydroxyiminopropionitrile is described, and the 3-hydrazono-2-hydroxyiminopropionitrile derivative of the present invention is a novel compound, and its production method has been completely known until now. Didn't.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、即
ち、新規な3-ヒドラゾノ-2-ヒドロキシイミノプロピオ
ニトリル誘導体及びその製法を提供するものである。The object of the present invention is to provide a novel 3-hydrazono-2-hydroxyiminopropionitrile derivative and a process for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明の課題は、一般式
（１）The object of the present invention is to solve the problems of the general formula (1):
【０００５】[0005]
【化４】 [Chemical 4]
【０００６】（式中、Ｒは、水素原子、置換基を有して
いても良いアルキル基又はアリール基を示す。）で示さ
れる3-ヒドラゾノ-2-ヒドロキシイミノプロピオニトリ
ル誘導体によって解決される。The problem is solved by a 3-hydrazono-2-hydroxyiminopropionitrile derivative represented by the formula (wherein R represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group). .
【０００７】本発明の課題は、又、式（２）The subject of the invention is also the formula (2)
【０００８】[0008]
【化５】 [Chemical 5]
【０００９】で示される2-ヒドロキシイミノ-3-オキソ
プロピオニトリルに、一般式（３）2-hydroxyimino-3-oxopropionitrile represented by the general formula (3)
【００１０】[0010]
【化６】 [Chemical 6]
【００１１】（式中、Ｒは、前記と同義である。）で示
されるヒドラジン化合物を反応させることを特徴とす
る、3-ヒドラゾノ-2-ヒドロキシイミノプロピオニトリ
ル誘導体の製法によっても解決される。The problem can also be solved by a method for producing a 3-hydrazono-2-hydroxyiminopropionitrile derivative, which comprises reacting a hydrazine compound represented by the formula (wherein R has the same meaning as defined above). .
【００１２】[0012]
【発明の実施の形態】本発明における3-ヒドラゾノ-2-
ヒドロキシイミノプロピオニトリル誘導体は、前記の一
般式（１）で示される。その一般式（１）において、Ｒ
は、水素原子、置換基を有していても良いアルキル基又
はアリール基を示す。前記のアルキル基としては、例え
ば、メチル基、エチル基、プロピル基、ブチル基、ペン
チル基、ヘキシル基、ヘプチル基等が挙げられ、前記の
アリール基としては、例えば、フェニル基、ピリジル
基、ピリミジル基、ピリダジル基等が挙げられる。な
お、これらの基は、各種異性体を含む。また、前記の置
換基としては、例えば、ヒドロキシル基；メチル基、エ
チル基、プロピル基、ブチル基等のアルキル基（これら
の基は、各種異性体を含む。）；メトキシル基、エトキ
シル基、プロポキシル基、ブトキシル基等のアルコキシ
ル基（これらの基は、各種異性体を含む。）；フッ素原
子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原
子；ニトロ基が挙げられる。又、置換基の位置や数は特
に限定されない。なお、該化合物はオキシム基、ヒドラ
ゾン基を有するため、Ｅ体やＺ体等、幾つかの異性体が
存在するが、いかなる異性体も含まれる。BEST MODE FOR CARRYING OUT THE INVENTION 3-hydrazono-2-of the present invention
The hydroxyiminopropionitrile derivative is represented by the above general formula (1). In the general formula (1), R
Represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. Examples of the alkyl group include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and the like, and examples of the aryl group include a phenyl group, a pyridyl group, and a pyrimidyl group. Group, pyridazyl group and the like. In addition, these groups include various isomers. Examples of the substituent include a hydroxyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group (these groups include various isomers); a methoxyl group, an ethoxyl group, and a propoxy group. And an alkoxyl group such as a group and a butoxyl group (these groups include various isomers); a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and a nitro group. Moreover, the position and number of the substituents are not particularly limited. Since the compound has an oxime group and a hydrazone group, there are some isomers such as E isomer and Z isomer, but any isomer is included.
【００１３】前記Ｒは、好ましくはヒドロキシル基で置
換されている炭素数１〜４のアルキル基、更に好ましく
はヒドロキシエチル基である。R is preferably an alkyl group having 1 to 4 carbon atoms, which is substituted with a hydroxyl group, and more preferably a hydroxyethyl group.
【００１４】3-ヒドラゾノ-2-ヒドロキシイミノプロピ
オニトリル誘導体は、一般式（４）The 3-hydrazono-2-hydroxyiminopropionitrile derivative has the general formula (4)
【００１５】[0015]
【化７】 [Chemical 7]
【００１６】（式中、Ｒは、前記と同義である。）で示
される工程によって5-アミノ-4-ニトロソピラゾール誘
導体に導くことが出来（後の参考例２に記載）、導かれ
た5-アミノ-4-ニトロソピラゾール誘導体は、毛髪染料
や、抗腫瘍剤の中間体として有用な4,5-ジアミノピラゾ
ール誘導体の合成原料として利用出来る（例えば、特開
昭60-56981号公報、特開昭62-273979号公報、特表平7-5
02542号公報）。(In the formula, R has the same meaning as above.) A 5-amino-4-nitrosopyrazole derivative can be obtained (described in Reference Example 2 below) and derived The -amino-4-nitrosopyrazole derivative can be used as a raw material for synthesizing a 4,5-diaminopyrazole derivative useful as an intermediate for hair dyes and antitumor agents (see, for example, JP-A-60-56981, JP-A-60-56981). Sho 62-273979 bulletin, special table 7-5
No. 02542).
【００１７】本発明の反応において使用する2-ヒドロキ
シイミノ-3-オキソプロピオニトリルは、前記の式
（２）で示されるが、これは、例えば、式（５）The 2-hydroxyimino-3-oxopropionitrile used in the reaction of the present invention is represented by the above formula (2), which is represented by, for example, the formula (5).
【００１８】[0018]
【化８】 [Chemical 8]
【００１９】で示されるように、3-メトキシアクリロニ
トリル及び／又は3,3-ジメトキシプロピオニトリルにニ
トロソ化剤を反応させることによって得られる化合物で
ある（後の参考例１に記載）。As shown in (3), it is a compound obtained by reacting 3-methoxyacrylonitrile and / or 3,3-dimethoxypropionitrile with a nitrosating agent (described in Reference Example 1 below).
【００２０】本発明の反応において使用するヒドラジン
化合物は、前記の一般式（３）で示される。その一般式
（３）において、Ｒは、前記と同義である。The hydrazine compound used in the reaction of the present invention is represented by the above general formula (3). In the general formula (3), R has the same meaning as described above.
【００２１】前記ヒドラジン化合物の使用量は、2-ヒド
ロキシイミノ-3-オキソプロピオニトリル1molに対し
て、好ましくは0.6〜5.0mol、更に好ましくは0.8〜2.0m
olである。The amount of the hydrazine compound used is preferably 0.6 to 5.0 mol, more preferably 0.8 to 2.0 m, per 1 mol of 2-hydroxyimino-3-oxopropionitrile.
ol.
【００２２】本発明の反応は、溶媒の存在下又は非存在
下で行われるが、溶媒を使用する場合には、反応を阻害
しないものならば特に限定されず、例えば、水；塩酸、
硫酸等の鉱酸類；メタノール、エタノール、イソプロピ
ルアルコール、n-ブチルアルコール、t-ブチルアルコー
ル等のアルコール類；アセトニトリル、プロピオニトリ
ル等のニトリル類；ヘキサン、ヘプタン等の脂肪族炭化
水素類；塩化メチレン、クロロホルム、四塩化炭素等の
ハロゲン化脂肪族炭化水素類；ベンゼン、トルエン等の
芳香族炭化水素類；クロロベンゼン等のハロゲン化芳香
族炭化水素類；ジエチルエーテル、ジイソプロピルエー
テル、テトラヒドロフラン、ジオキサン等のエーテル
類；酢酸、プロピオン酸等のカルボン酸類；N,N-ジメチ
ルホルムアミド、N,N-ジメチルアセトアミド等のアミド
類が挙げられるが、好ましくは水、鉱酸類、アルコール
類、エーテル類、更に好ましくはアルコール類、特に好
ましくはメタノールが使用される。なお、これらの溶媒
は、単独又は二種以上を混合して使用しても良い。The reaction of the present invention is carried out in the presence or absence of a solvent, and when a solvent is used, it is not particularly limited as long as it does not inhibit the reaction. For example, water; hydrochloric acid;
Mineral acids such as sulfuric acid; alcohols such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as hexane and heptane; methylene chloride , Halogenated aliphatic hydrocarbons such as chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane Carboxylic acids such as acetic acid and propionic acid; amides such as N, N-dimethylformamide and N, N-dimethylacetamide, but preferably water, mineral acids, alcohols and ethers, more preferably alcohol And particularly preferably methanol is used. It is. In addition, you may use these solvents individually or in mixture of 2 or more types.
【００２３】前記溶媒の使用量は、反応液の均一性や攪
拌性により適宜調節するが、2-ヒドロキシイミノ-3-オ
キソプロピオニトリル1gに対して、好ましくは0〜100
g、更に好ましくは0〜50gである。The amount of the solvent used is appropriately adjusted depending on the homogeneity and agitation property of the reaction solution, but is preferably 0 to 100 relative to 1 g of 2-hydroxyimino-3-oxopropionitrile.
g, and more preferably 0 to 50 g.
【００２４】本発明の反応は、例えば、窒素雰囲気に
て、2-ヒドロキシイミノ-3-オキソプロピオニトリル、
ヒドラジン化合物及び溶媒を混合して、攪拌しながら反
応させる等の方法によって行われる。その際の反応温度
は、好ましくは-30〜100℃、更に好ましくは-15〜50℃
であり、反応圧力は特に制限されない。The reaction of the present invention can be carried out, for example, in a nitrogen atmosphere by using 2-hydroxyimino-3-oxopropionitrile,
It is carried out by a method such as mixing a hydrazine compound and a solvent and reacting with stirring. The reaction temperature in that case is preferably -30 to 100 ° C, more preferably -15 to 50 ° C.
And the reaction pressure is not particularly limited.
【００２５】なお、本発明の反応では、塩酸等の酸を存
在させることによって、反応速度を高めることも出来
る。In the reaction of the present invention, the reaction rate can be increased by the presence of an acid such as hydrochloric acid.
【００２６】本発明の反応によって得られる3-ヒドラゾ
ノ-2-ヒドロキシイミノプロピオニトリル誘導体は、反
応終了後、例えば、濾過、抽出、濃縮、再結晶、晶析、
カラムクロマトグラフィー等の一般的な方法によって単
離・精製される。The 3-hydrazono-2-hydroxyiminopropionitrile derivative obtained by the reaction of the present invention is, for example, filtered, extracted, concentrated, recrystallized, crystallized, after the reaction is completed.
It is isolated and purified by a general method such as column chromatography.
【００２７】[0027]
【実施例】次に、実施例を挙げて本発明を具体的に説明
するが、本発明の範囲はこれらに限定されるものではな
い。EXAMPLES Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these.
【００２８】参考例１（2-ヒドロキシイミノ-3-オキソ
プロピオニトリルの合成）
攪拌装置、温度計、滴下漏斗及び冷却装置を備えた内容
積25mlのフラスコに、純度97％の3-メトキシアクリロニ
トリル2.0g(23mmol)及びジイソプロピルエーテル5mlを
加え、攪拌しながら-10℃まで冷却した。次いで、反応
液を5℃以下に保ちながら、濃塩酸3.5mlをゆるやかに添
加した。再び反応液を-10℃まで冷却後、亜硝酸ナトリ
ウム2.0g(36mmol)と水3mlの混合液をゆるやかに滴下
し、同温度で1.5時間、更に室温で2時間反応させた。反
応終了後、反応液を酢酸エチルで抽出した後に有機層を
分離し、飽和食塩水で洗浄後、無水硫酸マグネシウムで
乾燥させた。濾過後、反応液を減圧下で濃縮し、濃縮物
をシリカゲルカラムクロマトグラフィー（充填剤：Micr
o Sphere Gel D-150-60A、展開溶媒：トルエン/酢酸エ
チル=1/1(容量比)）で精製して、黄色油状物として2-ヒ
ドロキシイミノ-3-オキソプロピオニトリル2.3gを得た
(単離収率：100％)。更に、トルエンで再結晶させるこ
とで、淡黄色粉末として2-ヒドロキシイミノ-3-オキソ
プロピオニトリル0.79gを得た。なお、2-ヒドロキシイ
ミノ-3-オキソプロピオニトリルの物性値は以下の通り
である。Reference Example 1 (Synthesis of 2-hydroxyimino-3-oxopropionitrile) In a flask having an internal volume of 25 ml equipped with a stirrer, a thermometer, a dropping funnel and a cooling device, 3-methoxyacrylonitrile having a purity of 97% was used. 2.0 g (23 mmol) and 5 ml of diisopropyl ether were added, and it cooled to -10 degreeC, stirring. Next, 3.5 ml of concentrated hydrochloric acid was slowly added while maintaining the reaction liquid at 5 ° C or lower. After cooling the reaction solution again to -10 ° C, a mixed solution of 2.0 g (36 mmol) of sodium nitrite and 3 ml of water was slowly added dropwise, and the reaction was carried out at the same temperature for 1.5 hours and further at room temperature for 2 hours. After completion of the reaction, the reaction solution was extracted with ethyl acetate, the organic layer was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the reaction solution was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography (filler: Micr
o Sphere Gel D-150-60A, developing solvent: toluene / ethyl acetate = 1/1 (volume ratio)) to obtain 2-hydroxyimino-3-oxopropionitrile 2.3 g as a yellow oil.
(Isolated yield: 100%). Further, by recrystallizing from toluene, 0.79 g of 2-hydroxyimino-3-oxopropionitrile was obtained as a pale yellow powder. The physical properties of 2-hydroxyimino-3-oxopropionitrile are as follows.
【００２９】融点；76〜78℃
EI-MS(m/z)；98、53
CI-MS(m/z)；99(MH+)1
H-NMR(CDCl3，δ(ppm))；9.60(1H,s)、10.64(1H,s)
IR(KBr法、cm-1)；3129、2993、2831、1709、1457、142
8、1273、1076、768、745Melting point: 76 to 78 ° C. EI-MS (m / z); 98, 53 CI-MS (m / z); 99 (MH + ) 1 H-NMR (CDCl 3 , δ (ppm)); 9.60 (1H, s), 10.64 (1H, s) IR (KBr method, cm -1 ); 3129, 2993, 2831, 1709, 1457, 142
8, 1273, 1076, 768, 745
【００３０】実施例１（3-(2-ヒドロキシエチル)ヒドラ
ゾノ-2-ヒドロキシイミノプロピオニトリルの合成）
攪拌装置、温度計及び冷却装置を備えた内容積25mlのフ
ラスコに、参考例１と同様な方法で合成した2-ヒドロキ
シイミノ-3-オキソプロピオニトリル0.98g(10mmol)及び
メタノール6mlを加え、攪拌しながら5℃まで冷却した。
次いで、同温度で2-ヒドロキシエチルヒドラジン0.80g
(10mmol)を添加し、室温で1時間反応させた。反応終了
後、反応液を減圧下で濃縮し、濃縮物にヘキサンを加え
た後に、濾過して減圧下で乾燥させ、茶褐色固体として
3-(2-ヒドロキシエチル)ヒドラゾノ-2-ヒドロキシイミ
ノプロピオニトリル1.55gを得た(単離収率：99％)。な
お、3-(2-ヒドロキシエチル)ヒドラゾノ-2-ヒドロキシ
イミノプロピオニトリルは以下の物性値で示される新規
な化合物である。Example 1 (Synthesis of 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile) In a flask having an internal volume of 25 ml equipped with a stirrer, a thermometer and a cooling device, the same as in Reference Example 1 0.98 g (10 mmol) of 2-hydroxyimino-3-oxopropionitrile synthesized by any method and 6 ml of methanol were added, and the mixture was cooled to 5 ° C. with stirring.
Then, 0.80 g of 2-hydroxyethylhydrazine at the same temperature
(10 mmol) was added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure, hexane was added to the concentrate, filtered and dried under reduced pressure to obtain a brown solid.
1.55 g of 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile was obtained (isolated yield: 99%). In addition, 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile is a novel compound having the following physical properties.
【００３１】1H-NMR(DMSO-d6，δ(ppm))；3.17〜3.62(4
H,m)、4.42〜5.10(1H,brs)、7.33(0.2H,s)、7.53(0.8H,
s)、8.33(0.8H,t)、8.91(0.2Hz,t)、11.20〜13.10(1H,b
r) 1 H-NMR (DMSO-d 6 , δ (ppm)); 3.17 to 3.62 (4
H, m), 4.42 to 5.10 (1H, brs), 7.33 (0.2H, s), 7.53 (0.8H,
s), 8.33 (0.8H, t), 8.91 (0.2Hz, t), 11.20 to 13.10 (1H, b
r)
【００３２】参考例２（5-アミノ-1-(2-ヒドロキシエチ
ル)-4-ニトロソピラゾールの合成）
攪拌装置、温度計及び還流冷却器を備えた内容積25mlの
フラスコに、実施例１と同様な方法で合成した3-(2-ヒ
ドロキシエチル)ヒドラゾノ-2-ヒドロキシイミノプロピ
オニトリル0.94g(6mmol)及びn-ブチルアルコール6mlを
加え、110℃で3時間反応させた。反応終了後、反応液を
5℃まで冷却して1時間攪拌させると結晶が析出したの
で、結晶をを濾過し、濾過物を減圧下で乾燥させて、赤
橙色結晶として5-アミノ-1-(2-ヒドロキシエチル)-4-ニ
トロソピラゾール0.61gを得た(単離収率：64％)。な
お、5-アミノ-1-(2-ヒドロキシエチル)-4-ニトロソピラ
ゾールの物性値は以下の通りであった。Reference Example 2 (Synthesis of 5-amino-1- (2-hydroxyethyl) -4-nitrosopyrazole) A flask having an internal volume of 25 ml equipped with a stirrer, a thermometer and a reflux condenser was used as in Example 1. 0.94 g (6 mmol) of 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile synthesized in the same manner and 6 ml of n-butyl alcohol were added, and the mixture was reacted at 110 ° C. for 3 hours. After the reaction is complete,
Crystals were precipitated by cooling to 5 ° C. and stirring for 1 hour, so the crystals were filtered and the filtrate was dried under reduced pressure to give 5-amino-1- (2-hydroxyethyl) -as red-orange crystals. 0.61 g of 4-nitrosopyrazole was obtained (isolated yield: 64%). The physical properties of 5-amino-1- (2-hydroxyethyl) -4-nitrosopyrazole were as follows.
【００３３】融点；162.1〜167.3℃(dec.)1
H-NMR(DMSO-d6，δ(ppm))；3.66〜4.03(4H,m)、4.70〜
5.15(1H,br)、7.05(0.2H,s)、7.70〜8.37(2H,br)、8.54
(0.8H,s)Melting point: 162.1 to 167.3 ° C. (dec.) 1 H-NMR (DMSO-d 6 , δ (ppm)); 3.66 to 4.03 (4 H, m), 4.70 to
5.15 (1H, br), 7.05 (0.2H, s), 7.70-8.37 (2H, br), 8.54
(0.8H, s)
【００３４】[0034]
【発明の効果】本発明により、新規な3-ヒドラゾノ-2-
ヒドロキシイミノプロピオニトリル誘導体及びその製法
を提供することが出来る。According to the present invention, a novel 3-hydrazono-2-
A hydroxyiminopropionitrile derivative and a method for producing the same can be provided.
Claims (3)
ルキル基又はアリール基を示す。）で示される3-ヒドラ
ゾノ-2-ヒドロキシイミノプロピオニトリル誘導体。1. A general formula (1): (In the formula, R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group.) A 3-hydrazono-2-hydroxyiminopropionitrile derivative.
リルに、一般式（３） 【化３】 （式中、Ｒは、前記と同義である。）で示されるヒドラ
ジン化合物を反応させることを特徴とする、請求項１記
載の3-ヒドラゾノ-2-ヒドロキシイミノプロピオニトリ
ル誘導体の製法。2. Formula (2): 2-hydroxyimino-3-oxopropionitrile represented by the general formula (3) The method for producing a 3-hydrazono-2-hydroxyiminopropionitrile derivative according to claim 1, wherein a hydrazine compound represented by the formula (wherein R has the same meaning as defined above) is reacted.
素数１〜４のアルキル基である、請求項１又は２記載の
3-ヒドラゾノ-2-ヒドロキシイミノプロピオニトリル誘
導体及びその製法。3. The method according to claim 1 or 2, wherein R is an alkyl group having 1 to 4 carbon atoms, which is substituted with a hydroxyl group.
A 3-hydrazono-2-hydroxyiminopropionitrile derivative and a process for producing the same.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002101259A JP3873796B2 (en) | 2002-04-03 | 2002-04-03 | 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same |
| EP03701857A EP1475369A4 (en) | 2002-01-24 | 2003-01-24 | Process for producing 3-unsubstituted 5-amino-4-nitrosopyrazole compound, and 2-hydroxyimino-3-oxopropionitrile, 3-hydrazono-2-hydroxyiminopropionitrile compound, and processes for producing these |
| CN03802518.3A CN1284775C (en) | 2002-01-24 | 2003-01-24 | Process for producing 3-unsubstituted 5-amino-4-nitrosopyrazole compound, and 2-hydroxyimino-3-oxopropionitrile, 3-hydrazono-2-hydroxyiminopropionitrile compound, and processes for producing these |
| PCT/JP2003/000647 WO2003062207A1 (en) | 2002-01-24 | 2003-01-24 | Process for producing 3-unsubstituted 5-amino-4-nitrosopyrazole compound, and 2-hydroxyimino-3-oxopropionitrile, 3-hydrazono-2-hydroxyiminopropionitrile compound, and processes for producing these |
| US10/500,599 US7256304B2 (en) | 2002-01-24 | 2003-01-24 | Process for producing 3-unsubstituted 5-amino-4-nitrosopyrazole compound, and 2-hydroxyimino-3-oxopropionitrile, 3-hydrazono-2-hydroxyiminopropionitrile compound, and processes for producing these |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002101259A JP3873796B2 (en) | 2002-04-03 | 2002-04-03 | 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| JP3873796B2 JP3873796B2 (en) | 2007-01-24 |
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| Country | Link |
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