JPS58174369A - 1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparation - Google Patents
1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparationInfo
- Publication number
- JPS58174369A JPS58174369A JP5129983A JP5129983A JPS58174369A JP S58174369 A JPS58174369 A JP S58174369A JP 5129983 A JP5129983 A JP 5129983A JP 5129983 A JP5129983 A JP 5129983A JP S58174369 A JPS58174369 A JP S58174369A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- lower alkyl
- reaction
- hydroxypyrazole
- formula
- 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.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
本発明は新規な１−メチル−５−ハイドロキシピラゾー
ル−４−カルボン酸低級アルキルエステルおよびその製
造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel lower alkyl 1-methyl-5-hydroxypyrazole-4-carboxylic acid ester and a method for producing the same.
１−メチル−５−ハイドロキシピラゾール−４−カルボ
ン酸低級アルキルエステル（以下、単に本発明化合物ｉ
ｌｌという。）は１文献未載の新規化合物であり、農薬
、特に除草剤の有効成分化合物の中間体として有用な既
知化合物である１−メチル−５−ハイドロキシピラゾー
ル（以下、単に公知化合物Ａという。）の出発原料とし
て有用である。1-Methyl-5-hydroxypyrazole-4-carboxylic acid lower alkyl ester (hereinafter simply referred to as the present compound i)
It's called ll. ) is a new compound that has not been described in any literature, and is a compound of 1-methyl-5-hydroxypyrazole (hereinafter simply referred to as known compound A), which is a known compound useful as an intermediate for active ingredient compounds of agricultural chemicals, especially herbicides. Useful as a starting material.
従来、公知化合物ムの合成法としては１次の２つの方法
が知られている。Conventionally, two primary methods have been known as methods for synthesizing known compounds.
（１）２−メチル−１−（Ｐ−）ルエンスルホニル）−
３−ビンゾリドンを加水分解する方法〔ユルナリッシェ
・プラクティッシェ・ヒエミー（Ｊ。(1) 2-methyl-1-(P-)luenesulfonyl)-
3- Method for hydrolyzing vinzolidone [J.
ｐｒａｋｔ−ｃｈｅｍ ｌ第３１３巻第１１１８員＋１
９７１年）参照〕
（２）１−メチル−５−ハイド四キシピラゾールー５−
カルボン酸の熱分解による方法
〔ヒエミ・ペリヒテ（ｃｈｅｗ −Ｂ［Ｉｒｅ ）第１
０９ＩＩｋ第２６１買（１９７６年）参照〕
上記（１）の合成法は９反応工程が複雑であり、（２）
の合成法は、熱分解に極めで１温１１１１．．且つ□
収率が６Ｘ程度である。したがって、（１）および（２
）の合成法は、１−メチル−５−ハイドロキシピラゾー
ルを大量に合成する方法として満足で本発明者らは、１
−メチル−５−ハイドロキシピラゾールの有利な合成法
を種々検討した結果。prakt-chem l volume 313 number 1118 members +1
(2) 1-Methyl-5-hyde tetraxypyrazole-5-
Method by thermal decomposition of carboxylic acids [chew-B [Ire] No. 1
09IIk No. 261 Purchase (1976)] The synthesis method of (1) above has nine complicated reaction steps, and (2)
The synthesis method is extremely thermally decomposed at a temperature of 1111. ．． And □ Yield is about 6X. Therefore, (1) and (2
) is satisfactory as a method for synthesizing a large amount of 1-methyl-5-hydroxypyrazole, and the present inventors have determined that
- Results of various studies on advantageous synthetic methods of methyl-5-hydroxypyrazole.
低級アルコ命ジメチレンマロン酸ジ低級アルキルエステ
ルとメチルヒドラジンの閉場反応によって本発明化合物
である新規な１−メチル−５−ハイドロキシピラゾール
−４−カルボン酸低級アルキルエステル（１）を合成し
２次にこの化合物と鉱酸とを反応させて１−メチル−５
−ハイドロキシピラゾールを高収率で得る方法を見出し
友。A novel 1-methyl-5-hydroxypyrazole-4-carboxylic acid lower alkyl ester (1), which is a compound of the present invention, is synthesized by a closed field reaction of lower alkyl dimethylenemalonic acid di-lower alkyl ester and methylhydrazine, and then By reacting this compound with a mineral acid, 1-methyl-5
- Discovered a method to obtain hydroxypyrazole in high yield.
本発明者らが検討した反応を反応式で示せば次の通りで
ある。The reaction studied by the present inventors is shown in the following reaction formula.
賄
＋Ｉｌｌ 本発明化合物（１）□１
０Ｈ，ＣＨｌ
（１１公知化合物Ａ
（反応式中 Ｒ１およびＲ１は低級アルキル基１表わす
。）
上記反応工ｓ０）で示される反応は、無溶媒でも可能で
あるが、適当な有機１１ｍ（ｆＩえばメタノール、エタ
ノール等）中で行なうことが望ましい。反応温度は反応
開始時は低温が望ましく。+ Ill Compound of the present invention (1)□1 0H,CHl (11 Known compound A (In the reaction formula, R1 and R1 represent lower alkyl group 1) The reaction shown in the above reaction step s0) can be carried out without a solvent. However, it is preferable to carry out the reaction in a suitable organic solvent (for example, methanol, ethanol, etc.). The reaction temperature is preferably low at the start of the reaction.
反応終了時に近づくにつれて閉場反応【促進するために
′加熱することが望ましい。It is desirable to heat the closed-field reaction as it approaches the end of the reaction.
反応工８！←）で示される反応は１反応工程（イ）で得
られた本発明化合物（１）を原料として、この化合物と
鉱酸とを、水の存在下で加熱して、加水分解と脱炭酸反
応とを同時に行なって得られた生成物を中和して公知化
合物ムである１−メチル−５−ハイドロキシピラゾール
を得る。Reaction engineering 8! The reaction shown in ←) uses the compound (1) of the present invention obtained in reaction step 1 (a) as a raw material, and heats this compound and a mineral acid in the presence of water to perform hydrolysis and decarboxylation reactions. The resulting product is neutralized to obtain 1-methyl-5-hydroxypyrazole, a known compound.
本発明は一般式巾二
（式中 Ｒ１は低級アルキル基を示す。）で表わされる
１−メチル−５−ハイドロキシピラゾール−４−カルボ
ン酸低級アルキルエステルおよび
一般式（Ｈ）：
を示す。）
で表わされる低級アルコキシメチレンマロン酸ジ低級ア
ルキルエステルとメチルとドラジンとを反応させること
ｔ４Ｉ黴とする上記一般式（１）で表わされる化合物の
製造法に関するものである。The present invention represents a 1-methyl-5-hydroxypyrazole-4-carboxylic acid lower alkyl ester represented by the general formula (wherein R1 represents a lower alkyl group) and the general formula (H): The present invention relates to a method for producing a compound represented by the above general formula (1), which is obtained by reacting a lower alkoxymethylene malonic acid di-lower alkyl ester represented by the following with methyl and drazine to obtain t4I mold.
本発明において Ｒ１およびＲ１は１例えばメチル基。In the present invention, R1 and R1 are 1, for example, a methyl group.
エチル基、ｎ−プロピル基、１−プロピル基。Ethyl group, n-propyl group, 1-propyl group.
ｎ−ブチル基、 ５ｅｃ−ブチル基、ｔ−ブチル基な
どが挙げられる。Examples include n-butyl group, 5ec-butyl group, and t-butyl group.
本発明化合物の製造法においては、ｆｆｉ科のメチルヒ
ドラジン１モルに対し、一般式（ＩＩ）で表わされる化
合物のモール範囲としてα１〜１０モルでも可能である
が１％にα５〜２モルの範Ｓが望ましく、更に１モル前
後が好適である。In the method for producing the compound of the present invention, the mole range of the compound represented by general formula (II) can be α1 to 10 moles per mole of methylhydrazine of the ffi family, but α5 to 2 moles per 1%. S is desirable, and more preferably around 1 mol.
反応は、無溶媒でも可能であるが、遥轟な有機溶媒（例
えばメタノール、エタノ−ル等）中で行なうことが望ま
しい。反応温度は反応開始時は低温が望ましく１反応終
了時に近づくにつれて閉環反応【促進するために加熱す
ることが望ましい。Although the reaction can be carried out without a solvent, it is preferable to carry out the reaction in a strong organic solvent (for example, methanol, ethanol, etc.). The reaction temperature is desirably low at the start of the reaction, and as it approaches the end of one reaction, it is desirable to heat it to promote the ring-closing reaction.
本発明化合物を経由する本発明方法によれば。According to the method of the present invention via the compound of the present invention.
従来法に比べて予期し得ないほどＯＩＩ＆収皐で。Unexpectedly better OII & aphrodisiac compared to conventional methods.
且つ容易な操作で有用な公知化合物Ａｔ得ることができ
るという利点を有している。It also has the advantage that useful known compounds At can be obtained through easy operations.
次に１本発明について、実施例並びに参考ｆｉ＠を具体
的に挙げて説明する。但し１本発明はこれらのみに＠定
されるものではない。Next, one of the present invention will be explained by specifically citing examples and reference fi@. However, the present invention is not limited to these only.
実施ｆｉｉ１
１−メチル−５−ハイド−キシピラゾール−４−カルボ
ン酸エチルエステルＯ合成
エタノール５００ｄ及びエトキシメチレンマロン酸ジエ
チルエステル２１４２ｆ（１０モル）１、ｏ℃以下に冷
却し１反応温度ｔＯ℃以下に保持しながら、メチルヒド
ラジン４６ｆ（ｔ。Implementation fii1 1-Methyl-5-hyde-oxypyrazole-4-carboxylic acid ethyl ester O synthesis Ethanol 500d and ethoxymethylene malonic acid diethyl ester 2142f (10 mol) 1, cooled to below 0°C 1 Reaction temperature below tO°C While holding, methylhydrazine 46f (t.
モル）を滴下し友。滴下終了後、室温中で１時間攪拌し
１次いで１時間ｊｊｌｌｌＬ、た。反応終了後減圧下で
エタノールを留去し、１ｉＷｉｔ）ルエンで再結晶して
、標記目的化合物１４８？（１８７モル） ｆ得た。収
＄８７Ｘ 融点１５０〜１５６℃！
１−メチル−５−ハイ、ドロキシピラゾールの合成
実施例１で得た１−メチル−５−ハイドロキシヒラソー
ル−４−カルボン酸エチルエステル１７、 Ｏｆ （Ｃ
Ｌ １モル）ｔ、１：１希塩＠２００ｄ中に加えて２時
間還流した。 反応終了後。Drip a friend (mol). After the addition was completed, the mixture was stirred at room temperature for 1 hour, and then for 1 hour. After the reaction was completed, ethanol was distilled off under reduced pressure and recrystallized from toluene to obtain the title object compound 148? (187 mol) f was obtained. Yield $87X Melting point 150-156℃! Synthesis of 1-methyl-5-hydroxypyrazole 1-methyl-5-hydroxyhyrasole-4-carboxylic acid ethyl ester 17, Of (C
L 1 mol) t, 1:1 dilute salt@200d and refluxed for 2 hours. After the reaction is complete.
減圧下で留去、乾固し、残渣ｔイソプロピルアルコール
により再結晶して標記目的化合物の塩酸塩（融点１５５
〜１４７℃）管得た。その塩を炭酸水素カリウムで中和
して標記目的化合物ａ５Ｆ（（１０８７モル）を得た。The residue was evaporated to dryness under reduced pressure and recrystallized from isopropyl alcohol to give the hydrochloride of the title compound (melting point: 155
~147°C) tubes were obtained. The salt was neutralized with potassium hydrogen carbonate to obtain the title target compound a5F ((1087 mol)).
収率８７％特許出願人 日産化学工業株式金社Yield: 87% Patent applicant: Nissan Chemical Industries, Ltd.
Claims (2)
１−メチル−５−へイドロキシピラゾールー４−カルボ
ン酸低級アルキルエステル。(1) General formula (I): 1-methyl-5-hydroxypyrazole-4-carboxylic acid lower alkyl ester represented by (in the formula, R' is a lower alkyl group).
す。） で表わされる低級アルコキシメチレンマロン酸ジ低級ア
ルキルエステルとメチルヒドラジンとを反応させること
を脣徴とする 一般式（ｉ）： ＨＩ （式中、Ｒ”は前記と同じ意味ｔ−表わす。）で表わさ
れる１−メチル−５−ハイドロキシビラゾール−４−カ
ルボン酸低級アルキルエステルの製造法。(2) General formula + Ill: (In the formula, R1 and R'' each represent a lower alkyl group.) A general formula characterized by reacting a lower alkoxymethylene malonic acid di-lower alkyl ester represented by the following with methylhydrazine. (i): A method for producing 1-methyl-5-hydroxyvirazole-4-carboxylic acid lower alkyl ester represented by HI (in the formula, R'' has the same meaning as above and is represented by t-).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5129983A JPS58174369A (en) | 1983-03-26 | 1983-03-26 | 1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5129983A JPS58174369A (en) | 1983-03-26 | 1983-03-26 | 1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1917082A Division JPS58140073A (en) | 1982-02-09 | 1982-02-09 | Preparation of 1-methyl-5-hydroxypyrazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58174369A true JPS58174369A (en) | 1983-10-13 |
Family
ID=12883037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5129983A Pending JPS58174369A (en) | 1983-03-26 | 1983-03-26 | 1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174369A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3934924A1 (en) * | 1989-10-20 | 1991-04-25 | Huels Chemische Werke Ag | Prepn. of 4-alkoxy-carbonyl-3-chloro-methyl-2H-pyrazole derivs. - by reacting 3-alkoxy-methylene-4-chloro-3-oxo-butanoic acid ester with substd. hydrazine |
| US6329530B1 (en) | 1998-11-19 | 2001-12-11 | Basf Aktiengesellschaft | Method for the production of 1-substituted 5-hydroxypyrazoles |
| US6392058B1 (en) | 1998-11-19 | 2002-05-21 | Basf Aktiengesellschaft | Method for producing 1-substituted 5-Hydroxypyrazoles |
| JP2002371067A (en) * | 2001-06-15 | 2002-12-26 | Japan Hydrazine Co Inc | Method for producing 1-methyl-5-hydroxypyrazole |
| US6600071B2 (en) | 1998-11-05 | 2003-07-29 | Basf Aktiengesellschaft | Method for producing 1-substituted 5-hydroxpyrazoles |
| CN109320457A (en) * | 2018-10-12 | 2019-02-12 | 凯莱英医药化学（阜新）技术有限公司 | The preparation method and device of hydroxypyrazoles |
| CN112441978A (en) * | 2019-08-29 | 2021-03-05 | 江西天宇化工有限公司 | Preparation method of 1-methyl-5-hydroxypyrazole-4-carboxylic acid ethyl ester |
-
1983
- 1983-03-26 JP JP5129983A patent/JPS58174369A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3934924A1 (en) * | 1989-10-20 | 1991-04-25 | Huels Chemische Werke Ag | Prepn. of 4-alkoxy-carbonyl-3-chloro-methyl-2H-pyrazole derivs. - by reacting 3-alkoxy-methylene-4-chloro-3-oxo-butanoic acid ester with substd. hydrazine |
| DE3934924C2 (en) * | 1989-10-20 | 1994-01-27 | Huels Chemische Werke Ag | Process for the preparation of 4-alkoxycarbonyl-3-chloromethyl-2H-pyrazoles |
| US6600071B2 (en) | 1998-11-05 | 2003-07-29 | Basf Aktiengesellschaft | Method for producing 1-substituted 5-hydroxpyrazoles |
| US6329530B1 (en) | 1998-11-19 | 2001-12-11 | Basf Aktiengesellschaft | Method for the production of 1-substituted 5-hydroxypyrazoles |
| US6392058B1 (en) | 1998-11-19 | 2002-05-21 | Basf Aktiengesellschaft | Method for producing 1-substituted 5-Hydroxypyrazoles |
| JP2002371067A (en) * | 2001-06-15 | 2002-12-26 | Japan Hydrazine Co Inc | Method for producing 1-methyl-5-hydroxypyrazole |
| JP4641667B2 (en) * | 2001-06-15 | 2011-03-02 | 株式会社日本ファインケム | Process for producing 1-methyl-5-hydroxypyrazole |
| CN109320457A (en) * | 2018-10-12 | 2019-02-12 | 凯莱英医药化学（阜新）技术有限公司 | The preparation method and device of hydroxypyrazoles |
| CN112441978A (en) * | 2019-08-29 | 2021-03-05 | 江西天宇化工有限公司 | Preparation method of 1-methyl-5-hydroxypyrazole-4-carboxylic acid ethyl ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU1151211A3 (en) | Method of obtaining 5-aroyl-1,2-dihydro-3h-pyrrole /1,2-a/-pyrrole-1-carboxylic acid | |
| CA2103107C (en) | New amidation process | |
| Shi et al. | . delta.,. epsilon.-Unsaturated. beta.,. beta.-Difluoro-. alpha.-keto Esters: Novel Synthesis and Utility as Precursors of. beta.,. beta.-Difluoro-. alpha.-amino Acids | |
| JPS58174369A (en) | 1-methyl-5-hydroxypyrazole-4-carboxylic lower alkyl ester and its preparation | |
| JPS5929050B2 (en) | Production method of cyclohexanedione-(1,3) | |
| JPH10101627A (en) | Production of 3-amino-4,4,4-trihalocrotonate compound | |
| JPS58140073A (en) | Preparation of 1-methyl-5-hydroxypyrazole | |
| SU520032A3 (en) | The method of obtaining 2-nitrobenzaldehyde | |
| JPS58140074A (en) | Preparation of 1-methyl-5-hydroxypyrazole | |
| JPH0535145B2 (en) | ||
| JPH02292263A (en) | Production of 1-methyl-3-alkyl-5-pyrazole carboxylate | |
| HU214086B (en) | Process for producing 3-isoxazolecarboxylic acid and intermediates thereof | |
| JP4831897B2 (en) | Method for producing (2,6-dichloropyridin-4-yl) methanol | |
| JPS5927343B2 (en) | Synthesis method of 3-aminoisoxazoles | |
| JP2002371067A (en) | Method for producing 1-methyl-5-hydroxypyrazole | |
| JPH0158A (en) | 3-Amino-2,4,5-trifluorobenzoic acid and its production method | |
| RU2529190C1 (en) | Method of producing 2-hydroxy-2-carboxyalkyladamantanes | |
| JP2015131783A (en) | Method for producing aryl-1,2,4-triazole derivative | |
| JPH0665245A (en) | Production of pyridine-2,3-dicarboxylic anhydride | |
| SU925935A1 (en) | Process for producing aromatic aldimine | |
| CN116178265A (en) | Synthesis method of 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid | |
| JPH02282345A (en) | Production of 2,4,5-trifluorobenzoic acid | |
| Lizzi | Synthesis of Potential Insecticides and New Synthetic Applications of Vinamidinium and Azavinamidinium Salts: Reactions with Reducing Agents and Nitro Compounds | |
| JPH0925265A (en) | Production of carbodithioate derivative | |
| JPH0475230B2 (en) |