JP3676222B2 - Method for producing jasmonic ester derivative and its intermediate - Google Patents
Method for producing jasmonic ester derivative and its intermediate Download PDFInfo
- Publication number
- JP3676222B2 JP3676222B2 JP2000343789A JP2000343789A JP3676222B2 JP 3676222 B2 JP3676222 B2 JP 3676222B2 JP 2000343789 A JP2000343789 A JP 2000343789A JP 2000343789 A JP2000343789 A JP 2000343789A JP 3676222 B2 JP3676222 B2 JP 3676222B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- represented
- general formula
- amine
- compound
- 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
Links
- 0 *C(*)C(CC1)C(C(*)*2CC2)C1=O Chemical compound *C(*)C(CC1)C(C(*)*2CC2)C1=O 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、生理活性物質や香料の合成中間体として有用な２−アルキル−２−シクロペンテノンの製造法、及びそれを用いた、香料素材や生理活性物質として有用なジャスモン酸エステル誘導体の製造法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
２−アルキル−２−シクロペンテノンの製造法として、例えば、２−（１−ヒドロキシアルキル）−シクロペンタノンの脱水反応により２−アルキリデンシクロペンタノンを得た後、これを異性化する方法がある。その中では、２−アルキリデンシクロペンタノンにハロゲン化水素を接触させて２−アルキル−２−シクロペンテノンを製造する方法が知られており、その改良についても種々検討されている（特開昭５９−８０６２５号公報等）。
【０００３】
しかしながら、これらは低濃度の反応条件下でしか、高収率で目的物を得ることができず、工業化のためにさらなる改良が望まれていた。この改良方法として、ハロゲン化水素に代えアミンのハロゲン化水素塩を用いる方法も知られている（特開平６−８０６０６号公報）。しかしこの方法でも、溶媒を過剰に添加しないと十分満足できる収率が得られなかった。
【０００４】
また、２−（１−ヒドロキシアルキル）−シクロペンタノンから、脱水と異性化を一段階で行う方法も知られている（特開昭５６−１４７７４０号、特開平５−９２９３４号）。しかしながら、これらの方法は、反応に長時間を要する、収率が悪い、溶媒量が多く生産性が悪い等の欠点を有している。
【０００５】
本発明の課題は、生産効率の高い２−アルキル−２−シクロペンテノンの製造法、及びそれを用いたジャスモン酸エステル誘導体の製造法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明は、一般式（１）
【０００７】
【化６】
（式中、Ｒ1及びＲ2はそれぞれ水素原子又は炭素数１〜８の直鎖もしくは分岐鎖のアルキル基を示すか、あるいはＲ1とＲ2が一緒になって隣接する炭素原子と共にシクロペンタン環もしくはシクロヘキサン環を形成しても良い。）
で表される２−アルキリデンシクロペンタノン（以下化合物（１）という）に、アミンとハロゲン化水素とをアミン／ハロゲン化水素（モル比）＝１．１／１〜５／１の割合で作用させ、異性化反応を行う、一般式（２）
【０００９】
【化７】
（式中、Ｒ1及びＲ2は前記の意味を有する。）
で表される２−アルキル−２−シクロペンテノン（以下化合物（２）という）の製造法である。
【００１１】
また、本発明は、上記の製造法で得られた化合物（２）と、一般式（４）
【００１２】
【化８】
（式中、Ｒ3は炭素数１〜３の直鎖又は分岐鎖のアルキル基を示し、２個のＲ3は同一でも異なっていても良い。）
で表されるマロン酸ジエステル（以下化合物（４）という）とを反応させ、次いで水を反応させる、一般式（５）で表されるジャスモン酸エステル誘導体（以下化合物（５）という）の製造法である。
【００１４】
【化９】
（式中、Ｒ1、Ｒ2及びＲ3は前記の意味を有する。）
【００１６】
【発明の実施の形態】
［製造法１：化合物（１）から化合物（２）を得る製造法］
本発明に用いられる化合物（１）は、従来公知の方法により製造でき、例えばシクロペンタノンのエナミンとアルデヒドを脱水・縮合させ、その生成物を酸で分解する方法や、一般式（３）
【００１７】
【化１０】
（式中、Ｒ 1 及びＲ 2 は前記の意味を有する。）
で表される２−（１−ヒドロキシアルキル）−シクロペンタノン（以下化合物（３）という）を脱水する方法等により簡便に合成できる。
【００１９】
化合物（１）としては、２−ブチリデンシクロペンタノン、２−（２’−メチルブチリデン）シクロペンタノン、２−ペンチリデンシクロペンタノン、２−ヘキシリデンシクロペンタノン、２−シクロペンチリデンシクロペンタノン、２−シクロヘキシリデンシクロペンタノン、２−（１’−メチルブチリデン）−シクロペンタノン等が挙げられる。
【００２０】
本製造法に用いられるアミンとハロゲン化水素とは、低溶媒量でも高収率の化合物（２）を得るために、アミン／ハロゲン化水素（モル比）＝１．１／１〜５／１、好ましくは１．２／１〜３／１、より好ましくは１．５／１〜３／１の割合で反応させる。
【００２１】
本製造法に用いられるアミンは、弱塩基である芳香族アミン又は複素芳香環アミンが好ましく、具体的には、アニリン、ジフェニルアミン、ピリジン、ピコリン、キノリン、ポリビニルピリジン等が挙げられ、特にピリジン、ピコリン及びキノリンが好ましい。ハロゲン化水素としては、塩化水素、臭化水素又はヨウ化水素等が挙げられ、特に塩化水素又は臭化水素が好ましい。
【００２２】
アミンとハロゲン化水素とは、予めアミンとハロゲン化水素とを上記のようなアミン過剰の割合で混合したものを用いても、あるいは反応容器中にアミンとハロゲン化水素を上記割合で添加しても良い。ハロゲン化水素の使用量は、化合物（１）に対して、１〜50モル％、特に２〜20モル％が好ましい。
【００２３】
反応は、アルコール溶媒中又は無溶媒下で行うのが好ましい。アルコール溶媒としては、例えば炭素数１〜８の低級アルコール類、又はジオール類、トリオール類等が使用されるが、炭素数１〜８の低級アルコール類が特に好ましい。具体例としては、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ペンタノール、ヘキサノール、２−エチルヘキサノール、シクロヘキサノール、エチレングリコール、１，８−オクタンジオール、グリセリン、ポリエチレングリコール等が挙げられる。溶媒使用量は、化合物（１）に対し0.5〜５重量倍が好ましく、経済的には0.5〜２重量倍が更に好ましい。なお、反応溶媒は、使用する化合物（１）の物性により適宜選択されるが、選択された溶媒の沸点が反応温度以下である場合は、加圧下反応を行えばよい。
【００２４】
反応温度は80〜200℃、特に100〜180℃が好ましく、適当な時間反応させ、反応終了後常法に従って後処理をすることにより、化合物（２）が得られる。
【００２５】
反応手順としては、化合物（１）、溶媒、アミン及びハロゲン化水素を同時に仕込み反応させることもできるが、反応温度に達してから、触媒と化合物（１）を接触させることが好ましく、化合物（１）と溶媒を仕込み、そこへ所定の温度でアミン及びハロゲン化水素の混合液を滴下して反応させる方法、先に溶媒とアミン及びハロゲン化水素を仕込み、所定の温度で化合物（１）を滴下する方法等が挙げられるが、いずれの方法を採用してもよい。
【００２６】
化合物（１）の原料として用いられる化合物（３）において、１−ヒドロキシアルキル基を構成する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、イソプロピル基、ブチル基、イソブチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基等が挙げられる。
【００２７】
この化合物（３）は、従来公知の方法により製造でき、例えばシクロペンタノンと、式（６）
【００２８】
【化１１】
（式中、Ｒ1及びＲ2は前記の意味を有する。）
で表されるアルデヒド又はケトンを反応させることにより得ることができる。
【００３０】
［化合物（５）の製造法］
上記製造法１により得られた化合物（２）を原料とし、例えばＥＰ３３６０４号明細書に記載の方法により香料素材や生理活性物質として有用な化合物（５）を得ることができる。
【００３１】
具体的には、まず化合物（２）と化合物（４）とを塩基性触媒存在下に反応させ、一般式（７）で表される化合物（以下化合物（７）という）を得る。
【００３２】
【化１２】
（式中、Ｒ1、Ｒ2及びＲ3は前記の意味を有する。）
化合物（２）に対して化合物（４）を、１〜５モル培、好ましくは１．２〜２モル培の割合で反応させることが好ましい。
【００３４】
塩基性触媒としては、ナトリウム、カリウム等のアルカリ金属、ナトリウムアルコキシド、カリウムアルコキシド等のアルカリ金属アルコキシド等が挙げられる。触媒の使用量は化合物（２）に対して、０．０２〜０．２モル倍が好ましい。溶媒としてはアルコール類等の極性溶媒が好ましい。反応温度は−１０℃〜３０℃の範囲が好ましく、０〜２０℃の範囲がより好ましい。
【００３５】
次に、得られた化合物（７）と水とを反応させることにより、化合物（５）を製造することができる。水は、化合物（７）に対して１〜３モル倍量を反応系中に滴下しながら反応させることが好ましい。反応温度は１５０〜２２０℃の範囲が好ましい。
【００３６】
【実施例】
実施例１
２−ペンチリデンシクロペンタノン19.0ｇ（0.125モル）を、ｎ−ブタノール19.0ｇに溶かし、130℃に昇温した後、同温度で３−ピコリン1.8ｇ(0.019モル）と35％塩酸1.3ｇ（0.013モル）の混合液を30分で滴下した。滴下終了後、同温度で3.5時間加熱攪拌した。反応終了後、室温まで冷却し、水酸化ナトリウム水溶液で中和した後、有機層をガスクロマトグラフィーで分析を行った［分析は、ＤＢ−ＷＡＸカラムを用い、標準物質としてトリデカンを加えて行った。昇温条件：60℃−５℃／min−220℃］。その結果、反応終了品中には、２−ペンチル−２−シクロペンテノンが15.8ｇ含まれていることがわかった（収率：83.2％）。
【００３７】
実施例２
３−ピコリン2.3ｇ（0.025モル）と35％塩酸1.3ｇ（0.013モル）の混合液を用いた以外は実施例１と同様にして２−ペンチル−２−シクロペンテノンを15.5ｇ得た（収率；81.7％）。
【００３８】
実施例３
３−ピコリン4.7ｇ（0.050モル）と35％塩酸1.3ｇ（0.013モル）の混合液を用いた以外は実施例１と同様にして２−ペンチル−２−シクロペンテノンを15.0ｇ得た（収率；78.6％）。
【００３９】
比較例１
３−ピコリン1.2ｇ（0.013モル）と35％塩酸1.3ｇ（0.013モル）の混合液を用いた以外は実施例１と同様にして２−ペンチル−２−シクロペンテノンを14.3ｇ得た（収率；75.2％）。
【００４０】
実施例４
ｎ−ヘキサノール82.2ｇに３−ピコリン15.09ｇ（0.16モル）と35％塩酸5.63ｇ（0.055モル）を混合し、160℃に昇温した後、同温度で２−ペンチリデンシクロペンタノン164.4ｇ（1.08モル）を２時間かけて、また、同時に35％塩酸を1.41ｇ（0.014モル）／ｈの速度で２時間滴下した。滴下終了後、同温度で35％塩酸は滴下を続けながら５時間加熱攪拌した。反応終了後、室温まで冷却し、水酸化ナトリウム水溶液で中和した後、有機層を実施例１と同様にして分析を行った結果、２−ペンチル−２−シクロペンテノンを148.3ｇ得た（収率；90.2％）。
【００４１】
実施例５
溶媒として２−エチルヘキサノール82.2ｇを用いた以外は実施例４と同様にして２−ペンチル−２−シクロペンテノンを144.7ｇ得た（収率；88.0％）。
【００４２】
実施例６
２−エチルヘキサノール100.0ｇに３−ピコリン5.44ｇ（0.058モル）と35％塩酸5.54ｇ（0.053モル）を混合し、140℃に昇温した後、同温度で２−ペンチリデンシクロペンタノン100.0ｇ（0.53モル）を２時間かけて滴下した。滴下終了後、同温度で２時間加熱攪拌した。反応終了後、室温まで冷却し、水酸化ナトリウム水溶液で中和した後、有機層を実施例１と同様にして分析を行った結果、２−ペンチル−２−シクロペンテノンを69.2ｇ得た（収率；86.0％）。
【００４３】
実施例７
３−ピコリン7.42ｇ（0.080モル）と35％塩酸5.54ｇ（0.053モル）を用い、実施例６に従い、滴下反応を行った。滴下終了後、同温度で５時間加熱攪拌した。反応終了後、室温まで冷却し、水酸化ナトリウム水溶液で中和した後、有機層を実施例１と同様にして分析を行った結果、２−ペンチル−２−シクロペンテノンを65.2ｇ得た（収率；80.8％）。
【００４４】
実施例８
窒素雰囲気下、マロン酸ジメチル２３６ｇ（1.8mol）を無水メタノール７６ｇに溶解し、０℃に冷却した。そこに、ナトリウムメトキシド（３０％メタノール溶液）１２．９ｇ（0.072mol）を添加した後、実施例１と同様に合成して得られた２−ペンチル−２−シクロペンテノン１９０ｇ（1.2mol）を０℃で、２時間かけて滴下した。滴下終了後、未反応のマロン酸ジメチルを減圧留去し、３２０ｇのマイケル付加物を得た。
【００４５】
蒸留留出管をつけた反応装置に、上記で得られたマイケル付加物を加え、２１５℃に加熱し、水を6.4ｇ／ｈ（２％／ｈ）の速度で滴下した。発生する二酸化炭素とメタノールを留出させながら、２１５℃で、４時間滴下反応を行った。反応終了後、粗生成物２５１ｇ中に、３−オキソ−２−ペンチルシクロペンチル酢酸メチル２４５ｇを得た（２工程収率７６％）。
【００４６】
粗生成物を精留して得られた３−オキソ−２−ペンチルシクロペンチル酢酸メチルは、フルーティでジャスミン様の香気を有しており、香料素材としても優れたものであった。
【００４７】
【発明の効果】
本発明の方法によると溶媒を過剰に添加しなくても、高収率で２−アルキル−２−シクロペンテノンを得ることができる。また、この方法で得られた２−アルキル−２−シクロペンテノンを原料として用い、効率的にジャスモン酸エステル誘導体を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 2-alkyl-2-cyclopentenone useful as a synthetic intermediate for physiologically active substances and fragrances, and production of jasmonate derivatives useful as fragrance materials and physiologically active substances using the same. Regarding the law.
[0002]
[Prior art and problems to be solved by the invention]
As a method for producing 2-alkyl-2-cyclopentenone, for example, 2-alkylidenecyclopentanone is obtained by dehydration reaction of 2- (1-hydroxyalkyl) -cyclopentanone and then isomerized. is there. Among them, a method for producing 2-alkyl-2-cyclopentenone by contacting 2-alkylidenecyclopentanone with a hydrogen halide is known, and various improvements have been studied (Japanese Patent Laid-Open No. Sho). 59-80625).
[0003]
However, these products can only be obtained in high yield under low concentration reaction conditions, and further improvements have been desired for industrialization. As an improved method, a method using a hydrogen halide salt of an amine instead of a hydrogen halide is also known (Japanese Patent Laid-Open No. 6-80606). However, even with this method, a sufficiently satisfactory yield could not be obtained unless an excessive amount of solvent was added.
[0004]
Also known is a method in which dehydration and isomerization are carried out in one step from 2- (1-hydroxyalkyl) -cyclopentanone (Japanese Patent Laid-Open Nos. 56-147740 and 5-92934). However, these methods have drawbacks such as a long reaction time, a low yield, a large amount of solvent and poor productivity.
[0005]
An object of the present invention is to provide a method for producing 2-alkyl-2-cyclopentenone having high production efficiency and a method for producing a jasmonate derivative using the same.
[0006]
[Means for Solving the Problems]
The present invention relates to a general formula (1)
[0007]
[Chemical 6]
(In the formula, R 1 and R 2 each represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, or R 1 and R 2 together form a cyclopentane together with an adjacent carbon atom. A ring or a cyclohexane ring may be formed.)
In the case of 2-alkylidenecyclopentanone represented by the following formula (1), an amine and a hydrogen halide are reacted in a ratio of amine / hydrogen halide (molar ratio) = 1.1 / 1 to 5/1. And carrying out the isomerization reaction, general formula (2)
[0009]
[Chemical 7]
(In the formula, R 1 and R 2 have the above-mentioned meanings.)
Is a process for producing 2-alkyl-2-cyclopentenone (hereinafter referred to as compound (2)) .
[0011]
The present invention also provides the compound (2) obtained by the above production method and the general formula (4).
[0012]
[Chemical 8 ]
(In the formula, R 3 represents a linear or branched alkyl group having 1 to 3 carbon atoms, and two R 3 s may be the same or different.)
A method for producing a jasmonic acid ester derivative represented by the general formula (5) (hereinafter referred to as compound (5)), which is reacted with a malonic acid diester represented by general formula (hereinafter referred to as compound (4)) and then reacted with water. It is.
[0014]
[Chemical 9 ]
(Wherein R 1 , R 2 and R 3 have the above-mentioned meanings)
[0016]
DETAILED DESCRIPTION OF THE INVENTION
[Production Method 1: Production Method for Obtaining Compound (2) from Compound (1)]
The compound (1) used in the present invention can be produced by a conventionally known method. For example, a method of dehydrating and condensing an enamine of cyclopentanone and an aldehyde and decomposing the product with an acid, or a general formula (3)
[0017]
Embedded image
(In the formula, R 1 and R 2 have the above-mentioned meanings.)
It can be simply synthesized by a method of dehydrating 2- (1-hydroxyalkyl) -cyclopentanone (hereinafter referred to as compound (3)) represented by:
[0019]
As the compound (1), 2-butylidenecyclopentanone, 2- (2′-methylbutylidene) cyclopentanone, 2-pentylidenecyclopentanone, 2-hexylidenecyclopentanone, 2-cyclopentyl Examples include lidenecyclopentanone, 2-cyclohexylidenecyclopentanone, 2- (1′-methylbutylidene) -cyclopentanone.
[0020]
The amine and hydrogen halide used in this production method are amine / hydrogen halide (molar ratio) = 1.1 / 1 to 5/1 in order to obtain a high yield of compound (2) even with a low solvent amount. , Preferably 1.2 / 1 to 3/1, more preferably 1.5 / 1 to 3/1.
[0021]
The amine used in the present production method is preferably an aromatic amine or a heteroaromatic amine which is a weak base, and specific examples include aniline, diphenylamine, pyridine, picoline, quinoline, polyvinylpyridine and the like, and particularly pyridine, picoline. And quinoline are preferred. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide and the like, and hydrogen chloride or hydrogen bromide is particularly preferable.
[0022]
The amine and hydrogen halide may be prepared by mixing the amine and hydrogen halide in advance in the above-described proportion of excess amine, or by adding the amine and hydrogen halide in the above proportion in the reaction vessel. Also good. The amount of hydrogen halide used is preferably from 1 to 50 mol%, particularly preferably from 2 to 20 mol%, relative to compound (1).
[0023]
The reaction is preferably performed in an alcohol solvent or in the absence of a solvent. As the alcohol solvent, for example, lower alcohols having 1 to 8 carbon atoms, or diols, triols and the like are used, and lower alcohols having 1 to 8 carbon atoms are particularly preferable. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, 1,8-octanediol, glycerin, polyethylene glycol, and the like. . The amount of the solvent used is preferably 0.5 to 5 times by weight, more preferably 0.5 to 2 times by weight relative to the compound (1). The reaction solvent is appropriately selected depending on the physical properties of the compound (1) to be used. When the boiling point of the selected solvent is not higher than the reaction temperature, the reaction may be performed under pressure.
[0024]
The reaction temperature is preferably from 80 to 200 ° C., particularly preferably from 100 to 180 ° C. The compound (2) is obtained by reacting for an appropriate period of time and post-treatment according to a conventional method after completion of the reaction.
[0025]
As the reaction procedure, compound (1), solvent, amine and hydrogen halide can be charged and reacted at the same time. However, it is preferable to contact the catalyst with compound (1) after reaching the reaction temperature. ) And a solvent, and a mixture of amine and hydrogen halide is added dropwise at a predetermined temperature to cause a reaction. First, the solvent, amine and hydrogen halide are first added, and compound (1) is added dropwise at a predetermined temperature. However, any method may be adopted.
[0026]
In the compound (3) used as a raw material for the compound (1), examples of the alkyl group constituting the 1-hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and an amyl group. , Isoamyl group, hexyl group, heptyl group and the like.
[0027]
This compound (3) can be produced by a conventionally known method. For example, cyclopentanone and formula (6)
[0028]
Embedded image
(In the formula, R 1 and R 2 have the above-mentioned meanings.)
It can obtain by making the aldehyde or ketone represented by these react.
[0030]
[Production Method of Compound (5)]
A compound (5) useful as a fragrance material or a physiologically active substance can be obtained by using, for example, the method described in EP 33604, using the compound (2) obtained by the production method 1 as a raw material.
[0031]
Specifically, compound (2) and compound (4) are first reacted in the presence of a basic catalyst to obtain a compound represented by general formula (7) (hereinafter referred to as compound (7)).
[0032]
Embedded image
(Wherein R 1 , R 2 and R 3 have the above-mentioned meanings)
It is preferable to react the compound (4) with the compound (2) at a ratio of 1 to 5 moles, preferably 1.2 to 2 moles.
[0034]
Examples of the basic catalyst include alkali metals such as sodium and potassium, alkali metal alkoxides such as sodium alkoxide and potassium alkoxide, and the like. The amount of the catalyst used is preferably 0.02 to 0.2 mol times the compound (2). As the solvent, polar solvents such as alcohols are preferable. The reaction temperature is preferably in the range of −10 ° C. to 30 ° C., more preferably in the range of 0 to 20 ° C.
[0035]
Next, the compound (5) can be produced by reacting the obtained compound (7) with water. Water is preferably reacted while dropping 1 to 3 moles of the compound (7) in the reaction system. The reaction temperature is preferably in the range of 150 to 220 ° C.
[0036]
【Example】
Example 1
19.0 g (0.125 mol) of 2-pentylidenecyclopentanone was dissolved in 19.0 g of n-butanol, heated to 130 ° C., and then 1.8 g (0.019 mol) of 3-picoline and 1.3 g of 35% hydrochloric acid ( 0.013 mol) was added dropwise in 30 minutes. After completion of dropping, the mixture was heated and stirred at the same temperature for 3.5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and neutralized with an aqueous sodium hydroxide solution, and then the organic layer was analyzed by gas chromatography [analysis was performed using a DB-WAX column and adding tridecane as a standard substance. . Temperature rising condition: 60 ° C-5 ° C / min-220 ° C]. As a result, it was found that 15.8 g of 2-pentyl-2-cyclopentenone was contained in the finished product (yield: 83.2%).
[0037]
Example 2
15.5 g of 2-pentyl-2-cyclopentenone was obtained in the same manner as in Example 1 except that a mixed solution of 2.3 g (0.025 mol) of 3-picoline and 1.3 g (0.013 mol) of 35% hydrochloric acid was used. Rate; 81.7%).
[0038]
Example 3
15.0 g of 2-pentyl-2-cyclopentenone was obtained in the same manner as in Example 1 except that a mixed solution of 4.7 g (0.050 mol) of 3-picoline and 1.3 g (0.013 mol) of 35% hydrochloric acid was used. Rate: 78.6%).
[0039]
Comparative Example 1
14.3 g of 2-pentyl-2-cyclopentenone was obtained in the same manner as in Example 1 except that 1.2 g (0.013 mol) of 3-picoline and 1.3 g (0.013 mol) of 35% hydrochloric acid were used. Rate; 75.2%).
[0040]
Example 4
After mixing 15.09 g (0.16 mol) of 3-picoline and 5.63 g (0.055 mol) of 35% hydrochloric acid with 82.2 g of n-hexanol, the temperature was raised to 160 ° C., and then 164.4 g of 2-pentylidenecyclopentanone at the same temperature ( 1.08 mol) was added dropwise over 2 hours and at the same time 35% hydrochloric acid was added dropwise at a rate of 1.41 g (0.014 mol) / h for 2 hours. After completion of the dropwise addition, 35% hydrochloric acid was heated and stirred at the same temperature for 5 hours while continuing the dropwise addition. After completion of the reaction, the reaction mixture was cooled to room temperature and neutralized with an aqueous sodium hydroxide solution, and then the organic layer was analyzed in the same manner as in Example 1. As a result, 148.3 g of 2-pentyl-2-cyclopentenone was obtained ( Yield; 90.2%).
[0041]
Example 5
144.7 g of 2-pentyl-2-cyclopentenone was obtained in the same manner as in Example 4 except that 82.2 g of 2-ethylhexanol was used as a solvent (yield: 88.0%).
[0042]
Example 6
3-Picoline (5.44 g, 0.058 mol) and 35% hydrochloric acid (5.54 g, 0.053 mol) were mixed with 2-ethylhexanol (100.0 g), the temperature was raised to 140 ° C., and 2-pentylidenecyclopentanone (100.0 g) at the same temperature. (0.53 mol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred with heating at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and neutralized with an aqueous sodium hydroxide solution. The organic layer was analyzed in the same manner as in Example 1. As a result, 69.2 g of 2-pentyl-2-cyclopentenone was obtained ( Yield; 86.0%).
[0043]
Example 7
The dropping reaction was carried out according to Example 6 using 7.42 g (0.080 mol) of 3-picoline and 5.54 g (0.053 mol) of 35% hydrochloric acid. After completion of the dropwise addition, the mixture was heated and stirred at the same temperature for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and neutralized with an aqueous sodium hydroxide solution, and then the organic layer was analyzed in the same manner as in Example 1. As a result, 65.2 g of 2-pentyl-2-cyclopentenone was obtained ( Yield; 80.8%).
[0044]
Example 8
Under a nitrogen atmosphere, 236 g (1.8 mol) of dimethyl malonate was dissolved in 76 g of anhydrous methanol and cooled to 0 ° C. To this was added 12.9 g (0.072 mol) of sodium methoxide (30% methanol solution), and then 190 g (1.2 mol) of 2-pentyl-2-cyclopentenone obtained by synthesis in the same manner as in Example 1. Was added dropwise at 0 ° C. over 2 hours. After completion of dropping, unreacted dimethyl malonate was distilled off under reduced pressure to obtain 320 g of Michael adduct.
[0045]
The Michael adduct obtained above was added to a reactor equipped with a distillation distillation tube, heated to 215 ° C., and water was added dropwise at a rate of 6.4 g / h (2% / h). While distilling off the generated carbon dioxide and methanol, a drop reaction was carried out at 215 ° C. for 4 hours. After completion of the reaction, 245 g of methyl 3-oxo-2-pentylcyclopentylacetate was obtained in 251 g of the crude product (2 step yield 76%).
[0046]
The methyl 3-oxo-2-pentylcyclopentyl acetate obtained by rectifying the crude product had a fruity and jasmine-like fragrance, and was excellent as a fragrance material .
[0047]
【The invention's effect】
According to the method of the present invention, 2-alkyl-2-cyclopentenone can be obtained in high yield without adding an excessive amount of solvent. Moreover, a jasmonic acid ester derivative can be efficiently produced using 2-alkyl-2-cyclopentenone obtained by this method as a raw material.
Claims (4)
で表される２−アルキリデンシクロペンタノンに、アミンとハロゲン化水素とをアミン／ハロゲン化水素（モル比）＝１．１／１〜５／１の割合で作用させ、異性化反応を行う、一般式（２）
で表される２−アルキル−２−シクロペンテノンの製造法。General formula (1)
In the 2-alkylidenecyclopentanone represented by the formula (1), an amine and a hydrogen halide are allowed to act at a ratio of amine / hydrogen halide (molar ratio) = 1.1 / 1 to 5/1 to carry out an isomerization reaction. General formula (2)
The manufacturing method of 2-alkyl- 2-cyclopentenone represented by these.
で表される２−（１−ヒドロキシアルキル）−シクロペンタノンを脱水して得られるものである請求項１又は２記載の製造法The 2-alkylidenecyclopentanone represented by the general formula (1) is represented by the general formula (3).
The process according to claim 1 or 2, which is obtained by dehydrating 2- (1-hydroxyalkyl) -cyclopentanone represented by formula (1).
で表されるマロン酸ジエステルとを反応させ、次いで水を反応させる、一般式（５）で表されるジャスモン酸エステル誘導体の製造法。
The manufacturing method of the jasmonic acid ester derivative represented by General formula (5) which makes the malonic acid diester represented by these, and then react with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000343789A JP3676222B2 (en) | 2000-03-15 | 2000-11-10 | Method for producing jasmonic ester derivative and its intermediate |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000071689 | 2000-03-15 | ||
| JP2000-71689 | 2000-03-15 | ||
| JP2000-71690 | 2000-03-15 | ||
| JP2000071690 | 2000-03-15 | ||
| JP2000343789A JP3676222B2 (en) | 2000-03-15 | 2000-11-10 | Method for producing jasmonic ester derivative and its intermediate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004379745A Division JP4216248B2 (en) | 2000-03-15 | 2004-12-28 | Method for producing jasmonic acid ester derivative and its intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001328965A JP2001328965A (en) | 2001-11-27 |
| JP3676222B2 true JP3676222B2 (en) | 2005-07-27 |
Family
ID=27342673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000343789A Expired - Fee Related JP3676222B2 (en) | 2000-03-15 | 2000-11-10 | Method for producing jasmonic ester derivative and its intermediate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3676222B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4615206B2 (en) * | 2002-12-26 | 2011-01-19 | 花王株式会社 | Method for producing cycloalkanone derivative |
| IL159318A (en) * | 2002-12-26 | 2008-03-20 | Kao Corp | Method for producing 2-(alkyl) cycloalkenone |
| JP4651959B2 (en) * | 2004-03-15 | 2011-03-16 | 花王株式会社 | Cycloalkanone-containing composition |
| JP4667027B2 (en) * | 2004-12-09 | 2011-04-06 | 旭化成イーマテリアルズ株式会社 | Process for producing cis-2,3-disubstituted cyclopentanone |
| EE05449B1 (en) * | 2006-05-25 | 2011-08-15 | As Prosyntest | (2-H-Droxy-3-oxo-cis-clopent-1-ene) - '' Esters of dic acid and the method from these substances (-) - R- and (+) - S -homocitric acid gamma-lactone and for the preparation of the corresponding salts of (-) - R- and (+) - S homocitric acid |
| JP5486210B2 (en) * | 2008-05-13 | 2014-05-07 | 花王株式会社 | Process for producing 2-alkyl-2-cycloalkene-1-one |
-
2000
- 2000-11-10 JP JP2000343789A patent/JP3676222B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001328965A (en) | 2001-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030229251A1 (en) | Production of 2-amino-2-[2- (4-alkylphenyl) ethyl] propane-1, 3-diols | |
| JP4115828B2 (en) | Preparation of 2- (alkylidene) cycloalkanone | |
| JP3676222B2 (en) | Method for producing jasmonic ester derivative and its intermediate | |
| US7057077B2 (en) | Method for producing 2- (alkyl) cycloalkenone | |
| EP1134210B1 (en) | Method for producing jasmonate derivatives and intermediates thereof | |
| EP1756027B1 (en) | Process for producing indenol esters or ethers | |
| JP4407896B2 (en) | Method for producing 2- (alkyl) cycloalkenone | |
| JP4216248B2 (en) | Method for producing jasmonic acid ester derivative and its intermediate | |
| CN107428648B (en) | Process for the preparation of compounds such as 3-arylbutyraldehyde useful for the synthesis of medetomidine | |
| JP3923677B2 (en) | Process for producing 2-alkyl-2-cyclopentenone | |
| JP4156462B2 (en) | Method for producing acetate derivative | |
| JPH0680606A (en) | Production of 2-alkyl-2-cyclopentenone | |
| TW436474B (en) | Process for the preparation of isopropyl-methyl-[2-(3-n-propoxyphenoxy)ethyl]amine | |
| US10807941B2 (en) | Process for the preparation of polysantol-type compounds | |
| JPH0892150A (en) | Production of 5(e), 8(z), 11(z)-tetradecatrien-2-one | |
| JP6782632B2 (en) | Method for producing acetoacetic ester alkali salt and method for producing aliphatic diketone | |
| JPH10251233A (en) | Production of methylquinolines | |
| JP3312414B2 (en) | Process for producing dienoic halides | |
| EP1948584B1 (en) | Process for the preparation of cyclopentanone derivatives | |
| JPH10265433A (en) | Production of phenylpropionic acid derivative | |
| JPS6148815B2 (en) | ||
| JPS58118536A (en) | Preparation of jasmones | |
| JP2002241337A (en) | Method of producing 6-methyl-4,6-heptadiene-2-one and 3,7-dimethyl-1,5,7-octatriene-3-ol | |
| JPS6254295B2 (en) | ||
| JPS6039659B2 (en) | Novel method for producing propargyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041102 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041228 |
|
| 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: 20050426 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050427 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 3676222 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090513 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090513 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100513 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110513 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110513 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120513 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130513 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140513 Year of fee payment: 9 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |