JPS6110532A - Production of cyclopentanecarboxylic acid chloride - Google Patents
Production of cyclopentanecarboxylic acid chlorideInfo
- Publication number
- JPS6110532A JPS6110532A JP13041884A JP13041884A JPS6110532A JP S6110532 A JPS6110532 A JP S6110532A JP 13041884 A JP13041884 A JP 13041884A JP 13041884 A JP13041884 A JP 13041884A JP S6110532 A JPS6110532 A JP S6110532A
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- Japan
- Prior art keywords
- parts
- water
- base
- reaction
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野〕
本発明はシクロペンタンカルボン酸塩化合物の新規な製
造法に関し、さらに詳しくは、水及び有機溶剤の存在下
にファボルスキー反応せしめることによりシクロペンタ
ンカルボン酸塩化合物を製造する方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a new method for producing cyclopentane carboxylate compounds, and more specifically, the present invention relates to a novel method for producing cyclopentane carboxylate compounds, and more specifically, it relates to a method for producing cyclopentane carboxylic acid salt compounds, and more specifically, to produce cyclopentane carboxylate compounds by Faborski reaction in the presence of water and an organic solvent. The present invention relates to a method for producing an acid salt compound.
(従来の技術)
従来、シクロペンタンカルボン酸ヲファボルスキー(F
avoreicli ) 転位反応により合成する方
法として、2−ハロゲノシクロヘキサノンをアルコール
溶剤下に水酸化アルカリと反応させる方法[A、Fav
ors+ky at V、 Bojoveky、 Bu
lx、 Soc。(Prior art) Conventionally, cyclopentanecarboxylic acid Wofaborski (F
As a synthesis method by rearrangement reaction, 2-halogenocyclohexanone is reacted with an alkali hydroxide in an alcohol solvent [A, Fav
ors+ky at V, Bojoveky, Bu
lx, Soc.
Chin、 Fromco、 18.615 (191
5) )、おるいはアルコール溶剤下にナトリウムアル
コラードと反応させる方法(Goheen and V
aughan、 OrgSyntheses、 59.
37(1959)、R,B、 LOftfield。Chin, Fromco, 18.615 (191
5) ), or a method of reacting with sodium alcoholade in an alcohol solvent (Goheen and V
aughan, OrgSyntheses, 59.
37 (1959), R.B. LOftfield.
、T、A、O,S、、 υ、 4707 (195
1) ]が知られている。これらはいずれも反応系内に
水がほとんど存在しないかあるいは全く存在しない状態
で該転位反応を行わせしめ、反応中間体として該カルボ
ン酸エステル化合物を経て、これを加水分解し、該カル
ボン酸化合物を得る方法である。, T, A, O, S,, υ, 4707 (195
1) ] is known. In both of these methods, the rearrangement reaction is carried out in the absence of almost or no water in the reaction system, and the carboxylic acid ester compound is used as a reaction intermediate, and this is hydrolyzed to form the carboxylic acid compound. This is the way to get it.
(発明が解決しようとする問題点)
しかしながら、これらの方法はエステルの加水分解工程
を経るため工程が複雑となり、電気、スチーム等のユー
ティリティコストが高(なるばかりでなく、アルコール
の多用、アルコラードの使用等原料コストも高く、加水
分解が必ずしも定量的でないためのロスも大きい。(Problems to be solved by the invention) However, these methods require a step of hydrolysis of ester, which makes the process complicated, and the utility costs such as electricity and steam are high (not only do they require a lot of alcohol, but they also require the use of alcohol). The cost of raw materials used is high, and the loss is also large because hydrolysis is not necessarily quantitative.
そこで本発明者らはこれら欠点を改良すべく鋭意検討を
進めた結果、水酸化ナトリウムのような安価な塩基を用
いる場合であっても、溶剤として水と有機溶剤を共存さ
せるときわめて効率よくファボルスキー反応が進行する
ことを見い出し、本発明を完成するに至った。Therefore, the present inventors conducted extensive studies to improve these drawbacks, and found that even when using an inexpensive base such as sodium hydroxide, Fabolski is extremely efficient when water and an organic solvent coexist as solvents. They discovered that the reaction progresses and completed the present invention.
(問題点を解決するための手段)
かくして本発明によれば、α−ノ・ログノンクロへキサ
ノン化合物を水及び有機溶剤の存在下に塩基と接触せし
めることによりシクロペンタンカルボン酸塩化合物を高
収率で得る方法が提供される。(Means for Solving the Problems) Thus, according to the present invention, a cyclopentanecarboxylate compound can be produced in high yield by contacting an α-nologone chlorohexanone compound with a base in the presence of water and an organic solvent. A method is provided to obtain it.
本発明において用いられる原料のα−ハロゲノシクロヘ
キサノン化合物としては、2−クロルフクロヘキサノン
、α−ブロムシクロヘキサノン、α−アイオド/クロヘ
キサノンなどがあり、これらのメチル置換体、エチル置
換体、グチル置換体などのアルキル置換体も同様に使用
しうる。Examples of the α-halogenocyclohexanone compound used as a raw material in the present invention include 2-chlorofuclohexanone, α-bromocyclohexanone, α-iodo/clohexanone, and methyl-substituted, ethyl-substituted, butyl-substituted products of these compounds. Alkyl substituents of may be used as well.
本発明においては、かかる原料を用いて水及び有機溶剤
の存在下に反応が行われる。用いられる有機浴剤は塩基
と容易に反応するものでなければ特に限定されるもので
はなく、その具体例として、例エバメタノール、エタノ
ール、ブタノール、へキサノール、オクタツール、ラウ
リルアルコールなどのごときアルコール類、ジエチルエ
ーテル、ジブチルエーテル、ジフェニルエーテル、テト
ラヒドロフランなどのエーテル類、アセトニトリル、ベ
ンゾニトリルなどのニトリル類、ベンゼン、トルエン、
キシレン、ヘキサン、シクロヘキサンなどの炭化水素類
などが例示される。これらは必要に応じて2種以上を混
合して用いることができる0これらの有機溶剤のなかで
も、極性溶剤、とくに疎水性のアルコール類を用いるこ
とが収率向上の見地から好ましい。In the present invention, the reaction is carried out using such raw materials in the presence of water and an organic solvent. The organic bath agent used is not particularly limited as long as it does not easily react with bases, and specific examples include alcohols such as evaporated methanol, ethanol, butanol, hexanol, octatool, and lauryl alcohol. , ethers such as diethyl ether, dibutyl ether, diphenyl ether, and tetrahydrofuran, nitriles such as acetonitrile and benzonitrile, benzene, toluene,
Examples include hydrocarbons such as xylene, hexane, and cyclohexane. These organic solvents can be used in combination of two or more types if necessary. Among these organic solvents, it is preferable to use polar solvents, particularly hydrophobic alcohols, from the viewpoint of improving the yield.
かかる有機溶剤の使用量は適宜選択しうるが、通常は原
料の2−ノ・ログノンクロへキサノン化合物に対して0
,5〜10重量倍、好ましくは1〜5重量倍であり、そ
の使用量が少なくなるにつれて反応の制御が困難となり
、また高沸点副生成が増大する〇
有機溶剤の添加方法は反応器内に最初から塩基水溶液と
存在させておくか、その一部又は全量を原料の2−ハロ
ゲノシクロヘキサノン化合物と同時に添加してもよい。The amount of such organic solvent to be used can be selected as appropriate, but it is usually 0 to 2-no-logonone-chlorohexanone compound as the raw material.
, 5 to 10 times by weight, preferably 1 to 5 times by weight, and as the amount used decreases, it becomes difficult to control the reaction and high boiling point by-products increase. The aqueous base solution may be present from the beginning, or part or all of it may be added simultaneously with the 2-halogenocyclohexanone compound as a raw material.
一方、本発明において用いられる水の使用量は適宜選択
すればよいが、通常は2−ノ・ロゲノシクロベンタノン
化合物に対して0.15〜3重量倍、好ましくは0.3
〜2重量倍であり、水の使用量が過度に大きくなると収
率低下をもたらすことがある。かかる水は、通常、塩基
の水溶液として供給されるが、必要に応じて塩基とは独
立に供給することもできる。On the other hand, the amount of water used in the present invention may be appropriately selected, but is usually 0.15 to 3 times the weight of the 2-logenocyclobentanone compound, preferably 0.3 times the amount of water used in the present invention.
~2 times by weight, and if the amount of water used is too large, the yield may decrease. Such water is usually supplied as an aqueous solution of a base, but it can also be supplied independently of the base if necessary.
本発明に用いられる塩基はファボルスキー反応で一般に
用いられるものであればいずれでもよく、その具体例と
して水酸化リチウム、水酸化ナトリウム、水酸化カリウ
ム等の水酸化アルカリ金属、炭酸ナトリウム、炭酸カリ
ウム、−重炭酸カリウムなどのごとき炭酸塩などが例示
され、なかでも水酸化アルカリ金属が賞月される。かか
る塩基は原料の2−ハロゲノシクロヘキサノン化合物に
対し、通常1〜6当量、好ましくは2〜4当量使用され
、10〜80重量係、好ましくは50〜60重量%水溶
液として用いられる。The base used in the present invention may be any base that is commonly used in Faborski reactions, and specific examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, sodium carbonate, potassium carbonate, - Carbonates such as potassium bicarbonate are exemplified, and alkali metal hydroxides are particularly preferred. Such a base is usually used in an amount of 1 to 6 equivalents, preferably 2 to 4 equivalents, based on the 2-halogenocyclohexanone compound as a raw material, and is used as an aqueous solution of 10 to 80% by weight, preferably 50 to 60% by weight.
本発明で採用される反応条件は格別制限されるものでは
ないが、通常は反応温度が10℃〜100℃、好ましく
は25°C〜80℃、大気圧下の反応条件で行われ、水
、有機溶剤及び塩基の存在下に2−ハロゲノシクロヘキ
サノン化合物が15分〜5時間、好ましくは50分〜6
時間にわたって添加される。Although the reaction conditions employed in the present invention are not particularly limited, the reaction temperature is usually 10°C to 100°C, preferably 25°C to 80°C, under atmospheric pressure, and water, The 2-halogenocyclohexanone compound is heated in the presence of an organic solvent and a base for 15 minutes to 5 hours, preferably 50 minutes to 6 hours.
Added over time.
反応終了後、生成したシクロペンタンカルボン酸塩化合
物は水相または有機相から常法に従って分離されろ。ま
た必要に応じて、単離せずに加水分解を行いシクロペン
タンカルボン酸化合物にすることもできる。After the reaction is complete, the cyclopentane carboxylate compound produced is separated from the aqueous or organic phase in a conventional manner. Furthermore, if necessary, the cyclopentanecarboxylic acid compound can be obtained by hydrolysis without isolation.
(発明の効果)
かくして本発明によれば、簡犀な操作で効率よくかつ安
価な塩基を用いてシクロペンタンカルボン酸塩化合物を
得ることができる。(Effects of the Invention) Thus, according to the present invention, a cyclopentane carboxylate compound can be obtained efficiently with simple operations and using an inexpensive base.
v下に実施例を挙げて本発明をさらに具体的に説明する
。なお実施例及び比較例中の部及びチはとくに断りのな
いかぎり重量基準である0実施例1
攪拌機及び冷却還流器のついたステンレス製反応器に水
酸化ナトリウム50%水溶液を200部(NaOH2,
5モル)及びルーへキサノール500部を入れ、大気圧
下、50”Cで攪拌しなから2−クロルシクロへキサノ
ン100部(0,75モル)を2時間かけて添加し反応
した。反応終了後、室温に冷却し、て水相と有機相を分
離し、シクロペンタンカルボン酸ナトリウムのルーへキ
サノール溶液700部を得た。The present invention will be explained in more detail with reference to Examples below. Note that parts and parts in Examples and Comparative Examples are based on weight unless otherwise specified.Example 1 In a stainless steel reactor equipped with a stirrer and a cooling reflux device, 200 parts of a 50% aqueous solution of sodium hydroxide (NaOH2,
5 mol) and 500 parts of roohexanol were added, and while stirring at 50"C under atmospheric pressure, 100 parts of 2-chlorocyclohexanone (0.75 mol) was added over 2 hours to react. After the reaction was completed. The mixture was cooled to room temperature and separated into an aqueous phase and an organic phase to obtain 700 parts of a solution of sodium cyclopentanecarboxylate in roohexanol.
次にシクロベンクンカルボン酸ナトリウ!、の収率を測
定するために、このルーへキサノール/J液の一部をと
り、これに20°Cに冷却しなから10チ塩酸をpH3
になるまで少しずつ加え、シクロベンクンカルボン酸に
転化し、これをガスクロマトグラフィーにより定量した
(シクロベンクンカルボン酸ナトリウムからシクロペン
タンカルボン酸への強酸による転化は定量的に進む〕。Next is sodium cyclobencune carboxylate! In order to measure the yield of , a portion of this Rouhexanol/J solution was taken, cooled to 20°C, and 10% hydrochloric acid was added to it at pH 3.
The mixture was added little by little until the amount of cyclobencune carboxylic acid was reached, converting it to cyclobencune carboxylic acid, which was quantitatively determined by gas chromatography (the conversion of sodium cyclobencune carboxylate to cyclopentane carboxylic acid by a strong acid proceeds quantitatively).
その結果、シクロペンタンカルボン酸ナトリウムのモル
収率は595俤であった。またこのンアボルスキー転位
反応において36%のアジポインが副生成物として得ら
れた。As a result, the molar yield of sodium cyclopentanecarboxylate was 595 yen. In addition, 36% of adipoint was obtained as a by-product in this N-Aborski rearrangement reaction.
さらに上記シクロペンタ7カルボン酸ナトリウムのルー
へキサノール溶液100部にアセトン500部を加えて
結晶を析出させ、この結晶を漣過して分離し、1昼夜8
0℃で減圧乾燥した。得られた結晶は8.7部あり、H
−NMR及び工Rスペクトルによりシクロペンタンカル
ボン酸ナトリウムであることを確認した。この定量法に
よるモル収率は593%であった。Further, 500 parts of acetone was added to 100 parts of the rhohexanol solution of sodium cyclopenta7carboxylate to precipitate crystals, and the crystals were filtered and separated.
It was dried under reduced pressure at 0°C. The obtained crystals were 8.7 parts, and H
-NMR and E-R spectrum confirmed that it was sodium cyclopentanecarboxylate. The molar yield by this quantitative method was 593%.
実施例2
実施例1と同様の反応器に水酸化ナトリウム40%水浴
液を200部(NaOH2,0モル)及びルーブタノー
ル200部、トルエン300ieJ。Example 2 Into the same reactor as in Example 1, 200 parts of a 40% sodium hydroxide water bath solution (2.0 moles of NaOH), 200 parts of rubutanol, and 300 ieJ of toluene were added.
れ、大気圧下、50℃で攪拌しなから2−クロルシクロ
へキサノン100部(0,75モル)’z2時間かけて
添加し反応した。反応終了後、水650部を加えて析出
塩を溶解しながら室温まで冷却し、水相と有機相を分離
し°Cシクロペンタンカルボン酸ナトリウム水溶液とし
て650部得た。Then, 100 parts (0.75 mol) of 2-chlorocyclohexanone was added to the mixture under stirring at 50 DEG C. under atmospheric pressure over 2 hours, and the mixture was reacted. After the reaction was completed, 650 parts of water was added to dissolve the precipitated salt while cooling to room temperature, and the aqueous phase and organic phase were separated to obtain 650 parts of an aqueous solution of sodium cyclopentanecarboxylate at °C.
この水溶液の一部をとり、実施例1と同様の方法でシク
ロペンタンカルボン酸ナトリウムのガスクロマトグラフ
ィーによる定量を行い、モル収率525係を得た。A portion of this aqueous solution was taken and sodium cyclopentanecarboxylate was quantitatively determined by gas chromatography in the same manner as in Example 1 to obtain a molar yield of 525.
実施例6
水酸化す) IJウム667%水溶液150部(↑Jp
、OR2,5モル)を用いること以外は実施例1ど同様
にし2て反応を行った。その結果、ガスクロマトグラフ
ィーによる定量でシクロペンタンカルボン酸ナトリウム
のモル収率は653%であった。Example 6 150 parts of IJum 667% aqueous solution (↑Jp
The reaction was carried out in the same manner as in Example 1, except that 2.5 mol of OR, 2.5 mol) was used. As a result, the molar yield of sodium cyclopentanecarboxylate was 653% as determined by gas chromatography.
実施例4
ルーへキサノールに代えてテトラヒドロフランを用いる
こと以外は実施例1と同様にして反応を行った。その結
果、ガスクロマトグラフィーによる定量でシクロペンタ
ンカルボン酸ナトリウムのモル収率は48.5%であっ
た。Example 4 A reaction was carried out in the same manner as in Example 1 except that tetrahydrofuran was used in place of roohexanol. As a result, the molar yield of sodium cyclopentanecarboxylate was 48.5% as determined by gas chromatography.
比較例1
攪拌機及び冷却還流器のついたステンレス製反応器にナ
トリウムエトキシド102部(15モル)、エタノール
500部を入れ、大気圧下、50℃で攪拌しなから2−
クロルシクロへキサノン100部(0,75モル)を2
時間かけて添加し反応した。Comparative Example 1 102 parts (15 moles) of sodium ethoxide and 500 parts of ethanol were placed in a stainless steel reactor equipped with a stirrer and a cooling reflux device, and the mixture was stirred at 50°C under atmospheric pressure.
100 parts (0.75 mol) of chlorocyclohexanone
It was added and reacted over time.
反応終了後、大気圧下、エタノールを留去した。After the reaction was completed, ethanol was distilled off under atmospheric pressure.
この反応によりシクロペンタンカルボン酸エチルエステ
ルが生成した。この反応により生成したエチルエステル
をエーテルで抽出し、ガスクロマトグラフィーで定量し
たモル収率は53チであった。This reaction produced cyclopentanecarboxylic acid ethyl ester. The ethyl ester produced by this reaction was extracted with ether, and the molar yield determined by gas chromatography was 53.
エタノール留去後、水500部を加え70℃で1時間加
熱し、エステルを加水分解した。この際、生成するエタ
ノールを除去するため200部のトルエンで抽出したの
ち、実施例1と同様にしてシクロベンクンカルボン酸の
ガスクロマトグラフィーによる定量を行い、モル収率4
51%を得た。After distilling off the ethanol, 500 parts of water was added and heated at 70°C for 1 hour to hydrolyze the ester. At this time, after extraction with 200 parts of toluene to remove the ethanol produced, cyclobencune carboxylic acid was quantitatively determined by gas chromatography in the same manner as in Example 1, and the molar yield was 4.
Obtained 51%.
比較例2
攪拌機付きステンレス製反応器に水酸化ナトリウム50
チ水溶液200部(2,5モル)を入れ、大気圧下50
℃で攪拌しながら、2−クロルシクロへキサノン100
部(075モル)ヲ徐々に添加し反応した。この際、発
熱が著しく反応温度を制御するためにα−クロルシクロ
へキサノンの全量添加に4時゛間を要した。Comparative Example 2 Sodium hydroxide 50% in a stainless steel reactor equipped with a stirrer
Add 200 parts (2.5 mol) of an aqueous solution of
2-chlorocyclohexanone 100% while stirring at °C.
(075 mol) was gradually added and reacted. At this time, there was a great deal of heat generation, and in order to control the reaction temperature, it took 4 hours to add the entire amount of α-chlorocyclohexanone.
反応終了後、150部の水を加えて析出塩を溶解シ、シ
クロペンタンカルボン酸ナトリウム水溶液として450
部得九0生成物について実施例1と同様にしてガスクロ
マトグラフィーによる定量を行い、モル収率28.5
%を得た。After the reaction was completed, 150 parts of water was added to dissolve the precipitated salt, and 450 parts of sodium cyclopentanecarboxylate was prepared as an aqueous solution.
The obtained product was quantitatively determined by gas chromatography in the same manner as in Example 1, and the molar yield was 28.5.
I got %.
Claims (1)
溶剤の存在下に塩基と接触せしめることを特徴とするシ
クロペンタンカルボン酸塩化合物の製造法。1. A method for producing a cyclopentanecarboxylate compound, which comprises contacting a 1,2-halogenocyclohexanone compound with a base in the presence of water and an organic solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13041884A JPS6110532A (en) | 1984-06-25 | 1984-06-25 | Production of cyclopentanecarboxylic acid chloride |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13041884A JPS6110532A (en) | 1984-06-25 | 1984-06-25 | Production of cyclopentanecarboxylic acid chloride |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6110532A true JPS6110532A (en) | 1986-01-18 |
Family
ID=15033779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13041884A Pending JPS6110532A (en) | 1984-06-25 | 1984-06-25 | Production of cyclopentanecarboxylic acid chloride |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6110532A (en) |
-
1984
- 1984-06-25 JP JP13041884A patent/JPS6110532A/en active Pending
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