JPH0129782B2 - - Google Patents
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- JPH0129782B2 JPH0129782B2 JP55096333A JP9633380A JPH0129782B2 JP H0129782 B2 JPH0129782 B2 JP H0129782B2 JP 55096333 A JP55096333 A JP 55096333A JP 9633380 A JP9633380 A JP 9633380A JP H0129782 B2 JPH0129782 B2 JP H0129782B2
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- substituted
- acid
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- oxo
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明は一般式[Detailed description of the invention] The present invention is based on the general formula
【式】で表わされる
置換マロン酸ジエステル（式中R1は水素原子ま
たはアルキル基、R2は置換基を有することある
アルキル基またはシクロアルキル基、R3は低級
アルキル残基をそれぞれ表わす）から一般式From a substituted malonic acid diester represented by the formula (in the formula, R 1 is a hydrogen atom or an alkyl group, R 2 is an alkyl group or a cycloalkyl group that may have a substituent, and R 3 is a lower alkyl residue) general formula
【式】（式中R1、R2およびR3は前
記と同じ）で表わされる置換酢酸エステルの連続
的製造方法に関するものである。
さらに詳しくは、置換マロン酸ジエステルを特
定の酸性触媒の存在下に常圧で水と反応させて置
換酢酸とした後、引続き反応系にアルコールを添
加して反応を続せて置換酢酸エステルとするもの
である。
前記置換酢酸エステルには有用な香気物質、生
理活性を持つ化合物のみならず、近年とみに重要
性を増しているシスジヤスモン酸メチル、ブロス
タグランデイン合成中間体としても有用な物質が
含まれる。
これらの内、例えば、シスジヤスモン酸メチル
合成中間体である２−アルケニル−３−オキソ−
シクロペンチル酢酸エステルの製造方法に関して
はすでにいくつか知られている。
例えば、特公昭39−28240には２−アルキル−
３−オキソ−シクロペンチルマロン酸ジエステル
を酢酸および塩酸の混合物中で還流下に加熱し
て、ケン化、脱カルボキシル化させて２−アルキ
ル−３−オキソ−シクロペンチル酢酸とし、反応
系より該置換酢酸を単離して、濃硫酸、メタノー
ルと共に還流し、加熱し、生成物を抽出および蒸
留により反応系から分離する方法が開示されてい
る。
また特開昭48−64055には前記の置換マロン酸
ジエステルを加圧下、高温で水と処理して置換酢
酸を生成せしめ、反応系より置換酢酸を分離した
後、メタノールと反応させて目的に置換酢酸エス
テルを得る方法が開示されている。
この様に従来の方法においては、置換酢酸を先
ず反応系より分離してからアルコールと反応させ
てエステル化させねばならず、工程数が多くて複
雑であり、反応自体も高圧下であつたり、多量の
酸と接触させる等苛酷な条件を必要とするもので
ある。
本発明者等は、反応系から一旦置換酢酸を分離
することなく引き続きアルコールと反応させて置
換酢酸エステルとする簡単で、かつ高収率が得ら
れる方法を種々検討した結果、本発明に達したも
のである。
本発明の目的は置換マロン酸ジエステルを置換
酢酸エステルに変換させるに当り、反応条件もゆ
るやかであり、さらに複雑な工程を経ることなく
簡単な反応操作で脱カルボキシル化反応とエステ
ル化反応を連続して行わせて極めて収率よく置換
酢酸エステルを製造する方法を提供することにあ
る。
本発明のこの目的は一般式（）
（式中R1は水素原子またはアルキル基を表す。
R2は置換基を有することあるC1〜12のアルキル基
またはシクロアルキル基を表し、これらの基はカ
ルボニル基で修飾されているオキソ−アルキル基
またはオキソ−シクロアルキル基などを含む。
R3はC1〜4の低級アルキル基を表わす。以下も同
じ。）で表わされる置換マロン酸ジエステルと
（）に対して２倍モル以上の水とを、スルホン
酸系及びリン酸系触媒から選択される酸性触媒の
存在下に常圧、高温下に反応させ、置換酢酸
The present invention relates to a method for continuously producing a substituted acetate represented by the formula: (wherein R 1 , R 2 and R 3 are the same as above). More specifically, a substituted malonic acid diester is reacted with water at normal pressure in the presence of a specific acidic catalyst to form a substituted acetic acid, and then an alcohol is added to the reaction system to continue the reaction to form a substituted acetic acid ester. It is something. The substituted acetate esters include not only useful aroma substances and physiologically active compounds, but also substances useful as methyl cysdiasmonate and brostaglandein synthetic intermediates, which have become increasingly important in recent years. Among these, for example, 2-alkenyl-3-oxo- which is a synthetic intermediate of cis-methyl diasmonate
Several methods for producing cyclopentyl acetate are already known. For example, 2-alkyl-
3-oxo-cyclopentyl malonic acid diester is heated under reflux in a mixture of acetic acid and hydrochloric acid, saponified and decarboxylated to give 2-alkyl-3-oxo-cyclopentyl acetic acid, and the substituted acetic acid is removed from the reaction system. A method is disclosed in which the product is isolated, refluxed with concentrated sulfuric acid and methanol, heated, and the product is separated from the reaction system by extraction and distillation. Furthermore, in JP-A-48-64055, the above-mentioned substituted malonic acid diester is treated with water under pressure and high temperature to produce substituted acetic acid, and after separating the substituted acetic acid from the reaction system, it is reacted with methanol to obtain the desired substituted acetic acid. A method for obtaining acetate esters is disclosed. As described above, in the conventional method, substituted acetic acid must first be separated from the reaction system and then reacted with alcohol to esterify it, which is complicated with a large number of steps, and the reaction itself is under high pressure. It requires harsh conditions such as contact with a large amount of acid. The present inventors have arrived at the present invention as a result of various studies on a simple and high-yield method for producing a substituted acetic acid ester by subsequently reacting it with an alcohol without first separating the substituted acetic acid from the reaction system. It is something. The purpose of the present invention is to convert a substituted malonic acid diester into a substituted acetic acid ester under mild reaction conditions, and to perform the decarboxylation reaction and the esterification reaction sequentially through simple reaction operations without going through any complicated steps. The object of the present invention is to provide a method for producing substituted acetic esters with extremely high yield. This object of the invention is based on the general formula () (In the formula, R 1 represents a hydrogen atom or an alkyl group.
R2 represents a C1-12 alkyl group or cycloalkyl group which may have a substituent, and these groups include an oxo-alkyl group or an oxo-cycloalkyl group modified with a carbonyl group .
R 3 represents a C 1-4 lower alkyl group. The same applies below. ) A substituted malonic acid diester represented by () and water in an amount of twice or more moles relative to () are reacted at normal pressure and high temperature in the presence of an acidic catalyst selected from sulfonic acid-based and phosphoric acid-based catalysts, substituted acetic acid
【式】を生成せしめた後、引き続
き反応系に一般式R3OHで表わされるアルコール
を添加し、液相で反応させることによつて達成で
き、一般式（）
で表わされる置換酢酸エステルを高収率で製造す
ることができる。
次に本発明を更に詳しく説明する。
本発明で使用する出発原料である置換マロン酸
ジエステルは従来公知の方法で得ることができ
る。例えば、２−置換−３−オキソ−シクロペン
チルマロン酸ジエステルの場合は、２−置換−シ
クロペンテノンにナトリウムアルコキシドの存在
下、マロン酸ジエステルをマイケル付加させるこ
とにより容易に合成することができる。
本発明で使用する水の量は原料である置換マロ
ン酸ジエステルに対し2.0倍モル以上、好ましく
は３〜10倍モルの範囲である。
水の量が2.0倍モル未満の場合は反応が充分に
進行せず、また10倍モルを越えると、常圧下では
反応温度を好ましい範囲に保つことが困難とな
る。置換マロン酸ジエステルと水との反応は後記
する温度に加熱された置換マロン酸ジエステルへ
水を添加することによつて行わしめる。反応液へ
の水の添加方法は、連続的あるいは断続的に滴下
することにより、あるいは水あるいは水蒸気を反
応液中に吹き込む方法等を用いれば良い。水の添
加方法は反応液と水とが瞬時に接触することがで
きるものであればこれらに限定されるものではな
い。
置換マロン酸ジエステルと水との反応は、常圧
下、100〜300℃、特に好ましくは120〜250℃の温
度範囲で実施される。反応温度が低すぎると反応
速度は極めて遅くなり、充分な原料転換率が達成
できない。また、反応温度が高すぎると反応速度
は早くなるがタール状の副生成物が多くなり、反
応の選択率が低下する。
置換マロン酸ジエステルと水との反応で使用す
る酸性触媒は前記の反応温度範囲で安定であつ
て、揮発しないｐ−トルエンスルホン酸、カチオ
ン系イオン交換樹脂等のスルホン酸系触媒、ポリ
リン酸等のリン酸系触媒から選択される酸性触媒
である。塩酸、硫酸等の鉱酸では反応が充分に進
まず本発明の目的を達成することはできない。
置換マロン酸ジエステルと水との反応により置
換酢酸を生成せしめた後、置換酢酸を単離せず、
所望により酸性触媒を分離してから引き続いて反
応系にアルコールを添加して反応を続行し、副生
する水を留去しつゝ目的物質である置換酢酸エス
テルを合成する。
本発明で使用するアルコールは一般式R3OH
（R3はC1〜4のアルキル基）で表わされる低級アル
コールであり、原料である置換マロン酸ジエステ
ルに対し0.2〜200倍モル、好ましくは１〜50倍モ
ル、特に好ましくは10〜30倍モルの範囲で使用さ
れる。
反応液へのアルコールの添加方法は反応液とア
ルコールの接触が瞬時に行われる方法であれば何
等制限されないが、滴下あるいは液中吹き込み等
を連続的あるいは断続的に行う方法等が用いられ
る。反応は前記したと同じ温度範囲で実施され
る。反応は副生する水と共に未反応のアルコール
を反応系外に留去しつゝ行なわれ、アルコールは
乾燥後循環再使用することができる。
この様に本発明方法では、前段の置換酢酸の生
成は特定の酸性触媒を用いることにより、常圧で
実施でき、また前段反応終了の反応液へアルコー
ルを単に添加するだけで後段のエステル化反応も
容易に進行し、最後に蒸留操作により目的とする
置換酢酸エステルを高収率、高純度で回収するこ
とができる。
以上の如く本発明の方法によれば香料物質、医
薬、農薬またはそれらの合成中間体として有用な
置換酢酸エステルを簡単な操作で極めて収率良く
製造できるので、本発明は工業的に極めて有利な
方法と言うことができる。
以下に実施例により本発明を具体的に説明す
る。
参考例
乾燥メタノール150ｇ中に2.3ｇの金属ナトリウ
ムを加え完全に溶解する。この得られたナトリウ
ムメチラート溶液を−10℃に冷却し38.1ｇのマロ
ン酸ジメチルを加え30分間撹拌反応後15.2ｇの２
−ペンチリデンシクロペンタノンを加え1.5時間
撹拌反応させる。塩酸水溶液を添加し中和させた
後エーテル抽出を行い、エーテル層を蒸留するこ
とにより24.4ｇの２−ｎ−ペンチル−３−オキソ
−シクロペンチルマロン酸ジメチルを得る。収率
は２−ペンチリデンシクロペンタノン基準で86％
であつた。
実施例 １
２−ペンチル−３−オキソ−シクロペンチルマ
ロン酸ジメチル100ｇ及びパラトルエンスルホン
酸0.5ｇを還流弁付き精留管を備えたフラスコ内
に加え230℃に加熱する。精管管の環流弁を閉じ
たまゝ、この反応液中に水を反応液温度が200℃
以下とならない様徐々に滴下し、８時間で15ｇの
水を添加した。
その後、引き続き還流弁を開いてからメタノー
ルを20ｇ／時間の割合で反応液に添加した。留出
する未反応のメタノールは回収し、循環再使用し
た。10時間後メタノールの添加を終了し、反応を
終えた。
反応液を蒸留することにより２−ペンチル−３
−オキソ−シクロペンチル酢酸メチルを73.2ｇ得
た。収率は原料の２−ペンチル−３−オキソ−シ
クロペンチルマロン酸ジメチル基準で92％であつ
た。
尚、このものはIR、NMR、元素分析の結果よ
り目的物質の２−ペンチル−３−オキソ−シクロ
ペンチル酢酸メチルであることが確認された。
また、ガスクロマトグラフイー分析および酸価
測定の結果ジヒドロジヤスモン酸は検出されなか
つた。
前記の反応条件でパラトルエンスルホン酸0.5
ｇに代えてポリリン酸0.7ｇを用いる以外は全て
同一の条件で反応を行つた。この場合も２−ペン
チル−３−オキソ−シクロペンチル酢酸の収率は
92％であつた。
以上の結果、本発明方法は、前段で多量の塩酸
や酢酸を使用することもなく少量の触媒で常圧下
に加熱下の原料と水とを接触させ、後段は前段終
了後に反応系へ引き続きメタノールを添加するだ
けで良いので、極めてゆるやかな条件下、簡単な
反応操作で目的とする置換酢酸エステルが高収率
で得られる極めて優れた製造方法であることを示
している。
比較例 １
添加する水の量を6.4ｇとすることを以外は実
施例１と同様に反応を行つたところ、２−ペンチ
ル−３−オキソ−シクロペンチル酢酸メチルを
67.6ｇ得た。収率は原料の２−ペンチル−３−オ
キソ−シクロペンチルマロン酸ジメチル基準で85
％であつた。
比較例 ２
パラトルエンスルホン酸の代わりに硫酸を用い
ること以外は実施例１と同様に反応を行つたとこ
ろ、２−ペンチル−３−オキソ−シクロペンチル
酢酸メチルを62.9ｇ得た。収率は原料の２−ペン
チル−３−オキソ−シクロペンチルマロン酸ジメ
チル基準で79％であつた。またガスクロマトグラ
フイー分析及び酸価測定の結果ジヒドロジヤスモ
ン酸が6.3ｇ副生していることがわかつた。
酸触媒として硫酸のごとき鉱酸を用いると高沸
点副生物及び加水分解生成物を多量に与えること
がわかつた。After producing [Formula], this can be achieved by subsequently adding an alcohol represented by the general formula R 3 OH to the reaction system and reacting in the liquid phase. The substituted acetate represented by can be produced in high yield. Next, the present invention will be explained in more detail. The substituted malonic acid diester, which is the starting material used in the present invention, can be obtained by a conventionally known method. For example, 2-substituted-3-oxo-cyclopentyl malonic acid diester can be easily synthesized by Michael addition of malonic acid diester to 2-substituted cyclopentenone in the presence of sodium alkoxide. The amount of water used in the present invention is 2.0 times or more, preferably 3 to 10 times, by mole, relative to the substituted malonic acid diester as a raw material. If the amount of water is less than 2.0 times the mole, the reaction will not proceed sufficiently, and if it exceeds 10 times the mole, it will be difficult to maintain the reaction temperature within a preferred range under normal pressure. The reaction between the substituted malonic acid diester and water is carried out by adding water to the substituted malonic acid diester heated to the temperature described below. Water may be added to the reaction solution by dropping it continuously or intermittently, or by blowing water or steam into the reaction solution. The method of adding water is not limited to any method as long as the reaction solution and water can come into instant contact. The reaction of the substituted malonic acid diester with water is carried out under normal pressure at a temperature range of 100 to 300°C, particularly preferably 120 to 250°C. If the reaction temperature is too low, the reaction rate will be extremely slow, making it impossible to achieve a sufficient raw material conversion rate. On the other hand, if the reaction temperature is too high, the reaction rate will increase, but tar-like by-products will increase, and the selectivity of the reaction will decrease. The acidic catalyst used in the reaction of the substituted malonic acid diester with water is stable within the above reaction temperature range and does not volatilize, such as p-toluenesulfonic acid, sulfonic acid catalyst such as cationic ion exchange resin, polyphosphoric acid, etc. It is an acidic catalyst selected from phosphoric acid catalysts. Mineral acids such as hydrochloric acid and sulfuric acid do not allow the reaction to proceed sufficiently, making it impossible to achieve the object of the present invention. After producing substituted acetic acid by reaction of substituted malonic acid diester with water, without isolating the substituted acetic acid,
After separating the acidic catalyst if desired, alcohol is subsequently added to the reaction system to continue the reaction, and by-produced water is distilled off to synthesize the target substance, the substituted acetic ester. The alcohol used in the present invention has the general formula R 3 OH
(R 3 is a C 1-4 alkyl group), and is 0.2 to 200 times mole, preferably 1 to 50 times mole, particularly preferably 10 to 30 times the mole of substituted malonic acid diester as a raw material. Used in molar range. The method of adding alcohol to the reaction solution is not particularly limited as long as the reaction solution and alcohol are brought into contact instantly, but continuous or intermittent methods such as dropping or blowing into the solution can be used. The reaction is carried out in the same temperature range as described above. The reaction is carried out by distilling unreacted alcohol together with by-product water out of the reaction system, and the alcohol can be recycled and reused after drying. As described above, in the method of the present invention, the production of substituted acetic acid in the first stage can be carried out at normal pressure by using a specific acidic catalyst, and the subsequent esterification reaction can be carried out by simply adding alcohol to the reaction solution after the first stage reaction. The process also proceeds easily, and the desired substituted acetate ester can be recovered in high yield and purity by a final distillation operation. As described above, according to the method of the present invention, substituted acetate esters useful as fragrance substances, medicines, agricultural chemicals, or synthetic intermediates thereof can be produced with extremely high yield through simple operations. You can say it's a method. The present invention will be specifically explained below using Examples. Reference example Add 2.3g of metallic sodium to 150g of dry methanol and dissolve completely. The resulting sodium methylate solution was cooled to -10°C, 38.1 g of dimethyl malonate was added, and after stirring for 30 minutes, 15.2 g of dimethyl malonate was added.
- Add pentylidene cyclopentanone and react with stirring for 1.5 hours. After neutralization by adding an aqueous hydrochloric acid solution, ether extraction is performed, and the ether layer is distilled to obtain 24.4 g of dimethyl 2-n-pentyl-3-oxo-cyclopentylmalonate. Yield is 86% based on 2-pentylidenecyclopentanone
It was hot. Example 1 100 g of dimethyl 2-pentyl-3-oxo-cyclopentyl malonate and 0.5 g of para-toluenesulfonic acid are added to a flask equipped with a rectifying tube with a reflux valve and heated to 230°C. With the reflux valve of the vas deferens closed, water was added to the reaction solution until the temperature of the reaction solution reached 200°C.
The mixture was gradually added dropwise so as not to become too thick, and 15 g of water was added over 8 hours. Thereafter, the reflux valve was subsequently opened, and methanol was added to the reaction solution at a rate of 20 g/hour. The distilled unreacted methanol was collected and recycled for reuse. After 10 hours, the addition of methanol was completed and the reaction was completed. By distilling the reaction solution, 2-pentyl-3
73.2 g of methyl -oxo-cyclopentyl acetate was obtained. The yield was 92% based on the raw material dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. It was confirmed from the results of IR, NMR, and elemental analysis that this product was the target substance, methyl 2-pentyl-3-oxo-cyclopentylacetate. Further, as a result of gas chromatography analysis and acid value measurement, dihydrodiasmonic acid was not detected. 0.5 p-toluenesulfonic acid under the above reaction conditions.
The reaction was carried out under the same conditions except that 0.7 g of polyphosphoric acid was used instead of 0.7 g of polyphosphoric acid. In this case as well, the yield of 2-pentyl-3-oxo-cyclopentyl acetic acid is
It was 92%. As a result of the above, the method of the present invention does not require the use of large amounts of hydrochloric acid or acetic acid in the first stage, and brings the heated raw material into contact with water under normal pressure using a small amount of catalyst. This shows that it is an extremely excellent production method that allows the desired substituted acetate ester to be obtained in high yield under extremely mild conditions and with simple reaction operations. Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that the amount of water added was 6.4 g, and methyl 2-pentyl-3-oxo-cyclopentylacetate was
Obtained 67.6g. The yield is based on the raw material dimethyl 2-pentyl-3-oxo-cyclopentylmalonate.
It was %. Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that sulfuric acid was used instead of para-toluenesulfonic acid, and 62.9 g of methyl 2-pentyl-3-oxo-cyclopentylacetate was obtained. The yield was 79% based on the starting material dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. Further, as a result of gas chromatography analysis and acid value measurement, it was found that 6.3g of dihydrodiasmonic acid was produced as a by-product. It has been found that the use of mineral acids such as sulfuric acid as acid catalysts yields large amounts of high boiling by-products and hydrolysis products.
Claims (1)
は置換基を有することあるアルキル基またはシク
ロアルキル基を、R3は低級アルキル残基を表わ
す。以下同様）で表わされる置換マロン酸ジエス
テルと（）に対して２倍モル以上の水とをスル
ホン酸系及びリン酸系の触媒から選択される酸性
触媒の存在下に、常圧、高温下に反応せしめた
後、引き続き反応系に一般式R3OHで表わされる
低級アルコールを添加して反応を行わせることを
特徴とする一段反応による一般式（） で表わされる置換酢酸エステルの連続的製造方
法。[Claims] 1 General formula () (In the formula, R 1 is a hydrogen atom or an alkyl group, R 2
represents an alkyl group or a cycloalkyl group which may have a substituent, and R 3 represents a lower alkyl residue. A substituted malonic acid diester represented by General formula () by a one-step reaction characterized in that after the reaction, a lower alcohol represented by the general formula R 3 OH is subsequently added to the reaction system to carry out the reaction. A method for continuously producing a substituted acetate represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9633380A JPS5721340A (en) | 1980-07-15 | 1980-07-15 | Continuous preparation of substituted acetic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9633380A JPS5721340A (en) | 1980-07-15 | 1980-07-15 | Continuous preparation of substituted acetic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5721340A JPS5721340A (en) | 1982-02-04 |
| JPH0129782B2 true JPH0129782B2 (en) | 1989-06-14 |
Family
ID=14162080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9633380A Granted JPS5721340A (en) | 1980-07-15 | 1980-07-15 | Continuous preparation of substituted acetic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5721340A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL179368C (en) * | 1976-07-16 | 1986-09-01 | Roure Bertrand Dupont Sa | PROCESS FOR PREPARING OXOCYCLOPENTYL AND OXOCYCLOHEXYL COMPOUNDS. |
-
1980
- 1980-07-15 JP JP9633380A patent/JPS5721340A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5721340A (en) | 1982-02-04 |
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