JP3873796B2 - 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same - Google Patents

3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same Download PDF

Info

Publication number
JP3873796B2
JP3873796B2 JP2002101259A JP2002101259A JP3873796B2 JP 3873796 B2 JP3873796 B2 JP 3873796B2 JP 2002101259 A JP2002101259 A JP 2002101259A JP 2002101259 A JP2002101259 A JP 2002101259A JP 3873796 B2 JP3873796 B2 JP 3873796B2
Authority
JP
Japan
Prior art keywords
hydrazono
hydroxyiminopropionitrile
derivative
reaction
producing
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
Application number
JP2002101259A
Other languages
Japanese (ja)
Other versions
JP2003292478A (en
Inventor
泰久 福田
庄司 敷田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2002101259A priority Critical patent/JP3873796B2/en
Priority claimed from PCT/JP2003/000647 external-priority patent/WO2003062207A1/en
Publication of JP2003292478A publication Critical patent/JP2003292478A/en
Application granted granted Critical
Publication of JP3873796B2 publication Critical patent/JP3873796B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Description

【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。
【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.Geterotsikl.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。
【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。
【0004】
【課題を解決するための手段】
本発明の課題は、一般式(1)
【0005】
【化4】
【0006】
(式中、Rは、水素原子、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。
【0007】
本発明の課題は、又、式(2)
【0008】
【化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)
【0010】
【化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。
【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、ヒドロキシル基で置換されている炭素数1〜4のアルキル基又はアリール基を示す。前記の炭素数1〜4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、ヒドロキシル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。
【0013】
前記Rは、好ましくはヒドロキシエチル基である。
【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)
【0015】
【化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7-502542号公報)。
【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)
【0018】
【化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)。
【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。
【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0.8〜2.0molである。
【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。
【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0〜100g、更に好ましくは0〜50gである。
【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。
【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。
【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。
【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。
【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:Micro 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。
【0029】
融点;76〜78℃
EI-MS(m/z);98、53
CI-MS(m/z);99(MH+)
1H-NMR(CDCl3,δ(ppm));9.60(1H,s)、10.64(1H,s)
IR(KBr法、cm-1);3129、2993、2831、1709、1457、1428、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。
【0031】
1H-NMR(DMSO-d6,δ(ppm));3.17〜3.62(4H,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,br)
【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。
【0033】
融点;162.1〜167.3℃(dec.)
1H-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)
【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。
[0001]
BACKGROUND OF THE INVENTION
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 method for producing the same.
[0002]
[Prior art]
Conventionally, as a technique related to a 3-hydrazono-2-hydroxyiminopropionitrile derivative, Khim.Geterotsikl.Soedin., 7 , 976 (1991), 3- (β-dimethylhydrazono-α-oxyiminoethyl) Only a method for producing 3- (dimethylhydrazono) -2-hydroxyiminopropionitrile from 1,2,4-oxadiazol is described, and the 3-hydrazono-2-hydroxy of the present invention is described. The iminopropionitrile derivative is a novel compound and its production method has not been known at all.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel 3-hydrazono-2-hydroxyiminopropionitrile derivative and a process for producing the same.
[0004]
[Means for Solving the Problems]
The subject of this invention is general formula (1).
[0005]
[Formula 4]
[0006]
(Wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group substituted by a hydroxyl group ) and a 3-hydrazono-2-hydroxyiminopropionitrile derivative represented by The
[0007]
The subject of the present invention is also the formula (2)
[0008]
[Chemical formula 5]
[0009]
2-hydroxyimino-3-oxopropionitrile represented by the general formula (3)
[0010]
[Chemical 6]
[0011]
(In the formula, R is as defined above.)
It can also be solved by a method for producing a 3-hydrazono-2-hydroxyiminopropionitrile derivative, which is characterized by reacting a hydrazine compound represented by the formula:
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The 3- hydrazono- 2 -hydroxyiminopropionitrile derivative in the present invention is represented by the above general formula (1). In the general formula (1), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group substituted with a hydroxyl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group, a pyridyl group, a pyrimidyl group, and a pyridazyl group. Etc. These groups include various isomers. Moreover, the position and number of hydroxyl groups are not particularly limited. In addition, since this compound has an oxime group and a hydrazone group, several isomers such as E-form and Z-form exist, but any isomer is included.
[0013]
R is preferably a hydroxyethyl group.
[0014]
The 3-hydrazono-2-hydroxyiminopropionitrile derivative has the general formula (4)
[0015]
[Chemical 7]
[0016]
(In the formula, R is as defined above.)
Can be led to a 5-amino-4-nitrosopyrazole derivative (described in Reference Example 2 below), and the derived 5-amino-4-nitrosopyrazole derivative can be used as a hair dye or an antitumor agent. It can be used as a raw material for the synthesis of 4,5-diaminopyrazole derivatives useful as intermediates (for example, JP-A-60-56981, JP-A-62-273979, JP-A-7-502542).
[0017]
The 2-hydroxyimino-3-oxopropionitrile used in the reaction of the present invention is represented by the above formula (2).
[0018]
[Chemical 8]
[0019]
As shown in the above, 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]
The hydrazine compound used in the reaction of the present invention is represented by the general formula (3). In the general formula (3), R is as defined above.
[0021]
The amount of the hydrazine compound used is preferably 0.6 to 5.0 mol, more preferably 0.8 to 2.0 mol with respect to 1 mol of 2-hydroxyimino-3-oxopropionitrile.
[0022]
The reaction of the present invention is carried out in the presence or absence of a solvent. When a solvent is used, it is not particularly limited as long as it does not inhibit the reaction. For example, water; mineral acids such as hydrochloric acid and sulfuric acid Alcohols such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as hexane and heptane; methylene chloride, chloroform and tetrachloride Halogenated aliphatic hydrocarbons such as carbon; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; acetic acid and propion Carboxylic acids such as acids; N, N-dimethylformamide, N, N-dimethylacetate Although amides such as bromide and the like, preferably water, mineral acids, alcohols, ethers, more preferably alcohols, especially preferably used is methanol. In addition, you may use these solvents individually or in mixture of 2 or more types.
[0023]
The amount of the solvent used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 0 to 100 g, more preferably 0 to 50 g, relative to 1 g of 2-hydroxyimino-3-oxopropionitrile. is there.
[0024]
The reaction of the present invention is performed by, for example, a method of mixing 2-hydroxyimino-3-oxopropionitrile, a hydrazine compound and a solvent in a nitrogen atmosphere and reacting them with stirring. The reaction temperature at that time is preferably −30 to 100 ° C., more preferably −15 to 50 ° C., and the reaction pressure is not particularly limited.
[0025]
In the reaction of the present invention, the reaction rate can be increased by the presence of an acid such as hydrochloric acid.
[0026]
The 3-hydrazono-2-hydroxyiminopropionitrile derivative obtained by the reaction of the present invention can be obtained by a general method such as filtration, extraction, concentration, recrystallization, crystallization, column chromatography after completion of the reaction. Separated and purified.
[0027]
【Example】
Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
[0028]
Reference Example 1 (Synthesis of 2-hydroxyimino-3-oxopropionitrile)
To a 25-ml flask equipped with a stirrer, thermometer, dropping funnel and cooling device was added 2.0 g (23 mmol) of 97% pure 3-methoxyacrylonitrile and 5 ml of diisopropyl ether, and the mixture was cooled to -10 ° C. with stirring. . Subsequently, 3.5 ml of concentrated hydrochloric acid was slowly added while keeping the reaction solution at 5 ° C. or lower. The reaction solution was again cooled to −10 ° C., and a mixed solution of 2.0 g (36 mmol) of sodium nitrite and 3 ml of water was slowly added dropwise and reacted 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 is concentrated under reduced pressure, and the concentrate is purified by silica gel column chromatography (filler: Micro Sphere Gel D-150-60A, developing solvent: toluene / ethyl acetate = 1/1 (volume ratio)). As a result, 2.3 g of 2-hydroxyimino-3-oxopropionitrile was obtained as a yellow oil (isolation yield: 100%). Furthermore, recrystallization from toluene gave 0.79 g of 2-hydroxyimino-3-oxopropionitrile as a pale yellow powder.
The physical properties of 2-hydroxyimino-3-oxopropionitrile are as follows.
[0029]
Melting point: 76-78 ° 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, 1428, 1273, 1076, 768, 745
[0030]
Example 1 (Synthesis of 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile)
To a flask having an internal volume of 25 ml equipped with a stirrer, a thermometer and a cooling device, 0.98 g (10 mmol) of 2-hydroxyimino-3-oxopropionitrile synthesized in the same manner as in Reference Example 1 and 6 ml of methanol were added, Cooled to 5 ° C. with stirring. Next, 0.80 g (10 mmol) of 2-hydroxyethylhydrazine was added at the same temperature, 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, and 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropio was obtained as a brown solid. 1.55 g of nitrile was obtained (isolation yield: 99%).
Note that 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile is a novel compound represented by the following physical property values.
[0031]
1 H-NMR (DMSO-d 6 , δ (ppm)); 3.17 to 3.62 (4H, 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), 11.20-13.10 (1H, br)
[0032]
Reference Example 2 (Synthesis of 5-amino-1- (2-hydroxyethyl) -4-nitrosopyrazole)
To a flask having an internal volume of 25 ml equipped with a stirrer, a thermometer and a reflux condenser, 0.94 g (6 mmol) of 3- (2-hydroxyethyl) hydrazono-2-hydroxyiminopropionitrile synthesized in the same manner as in Example 1 was prepared. ) And 6 ml of n-butyl alcohol were added and reacted at 110 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to 5 ° C. and stirred for 1 hour, so that crystals precipitated. The crystals were filtered, and the filtrate was dried under reduced pressure to give 5-amino-1- 0.61 g of (2-hydroxyethyl) -4-nitrosopyrazole was obtained (isolation yield: 64%).
The physical properties of 5-amino-1- (2-hydroxyethyl) -4-nitrosopyrazole were as follows.
[0033]
Melting point: 162.1-167.3 ° C (dec.)
1 H-NMR (DMSO-d 6 , δ (ppm)); 3.66 to 4.03 (4H, m), 4.70 to 5.15 (1H, br), 7.05 (0.2H, s), 7.70 to 8.37 (2H, br) 8.54 (0.8H, s)
[0034]
【The invention's effect】
According to the present invention, a novel 3-hydrazono-2-hydroxyiminopropionitrile derivative and a method for producing the same can be provided.

Claims (3)

一般式(1)
(式中、Rは、水素原子、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。
General formula (1)
(Wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group substituted with a hydroxyl group ), a 3-hydrazono-2-hydroxyiminopropionitrile derivative.
式(2)
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)
(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。
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 is as defined above) is reacted.
Rが、ヒドロキシルエチル基である、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。The 3-hydrazono-2-hydroxyiminopropionitrile derivative according to claim 1, wherein R is a hydroxylethyl group.
JP2002101259A 2002-04-03 2002-04-03 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same Expired - Fee Related JP3873796B2 (en)

Priority Applications (1)

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

Applications Claiming Priority (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
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
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
CN 03802518 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
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

Publications (2)

Publication Number Publication Date
JP2003292478A JP2003292478A (en) 2003-10-15
JP3873796B2 true JP3873796B2 (en) 2007-01-24

Family

ID=29241721

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002101259A Expired - Fee Related JP3873796B2 (en) 2002-04-03 2002-04-03 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same

Country Status (1)

Country Link
JP (1) JP3873796B2 (en)

Also Published As

Publication number Publication date
JP2003292478A (en) 2003-10-15

Similar Documents

Publication Publication Date Title
JP4725977B2 (en) Process for producing 2-dihaloacyl-3-amino-acrylic acid ester and 3-dihalomethyl-pyrazole-4-carboxylic acid ester
JP6078563B2 (en) Process for preparing phenyl substituted 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N-methoxy- [1-methyl-2-phenylethyl] amide
EP1773783A1 (en) Method for preparing n-piperidino-1,5-diphenylpyrazole-3-carboxamide derivatives
JP3873796B2 (en) 3-hydrazono-2-hydroxyiminopropionitrile derivative and process for producing the same
TW477785B (en) Process for the preparation of 0-chloromethyl-phenylglyoxylic acid derivatives
JP4013772B2 (en) 2-Hydroxyimino-3-oxopropionitrile and process for producing the same
US7256304B2 (en) 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
JP3855686B2 (en) 3,3-dialkoxy-2-hydroxyimino derivative and process for producing the same
JP4158536B2 (en) Method for producing 3-unsubstituted-5-amino-4-nitrosopyrazole compound
JP2003300963A (en) Method for producing 5-amino-4-nitrosopyrazole derivative
JP4929717B2 (en) Process for producing N, N'-dialkoxy-N, N'-dialkyloxamide
EP1408025B1 (en) 3,3-dialkoxy-2-hydroxyiminopropionitriles, process for preparation thereof and process of preparing 5-amino -4-nitrosopyrazoles or salts thereof by the use of the same
JP4211274B2 (en) Process for producing 5-amino-4-nitrosopyrazole derivative or its acid salt
JP4126944B2 (en) Process for producing 5-amino-4-nitrosopyrazole compound
JP4828740B2 (en) Process for producing 1,2,5-thiadiazoylmethanone derivative and dioxime derivative
JP4507390B2 (en) 1-alkyl-1-substituted-3-organosulfonyloxyazetidinium salts and process for producing the same
JP2743441B2 (en) Cyclopenta [1,2-C] -3-pyrazolecarboxylic acid derivative
JP3819473B2 (en) 4,4-Bishalomethyl-3-oxoalkanecarboxylic acid derivative and method for producing 3-cyclopropyl-3-oxopropionic acid derivative using the same
JP2784920B2 (en) 1,3-cyclohexanedione derivative
JP2006524196A (en) A method for producing nicotinaldehyde.
JPWO2005061478A1 (en) Process for producing 4-alkoxycarbonyltetrahydropyran or tetrahydropyranyl-4-carboxylic acid
JP2002363171A (en) Method of producing 4-substituted-3-amino-isoxazole derivative
JP2004026652A (en) beta-ALKOXYACRYLONITRILE DERIVATIVE
JP2001335564A (en) Method for producing ester of 1-alkyl-5-substituted pyrazole-3-carboxylic acid
JP2002128766A (en) Method for manufacturing 5-substituted isooxazole

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20040819

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20060822

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20060828

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20060915

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20061003

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20061016

LAPS Cancellation because of no payment of annual fees