JP2000136153A - Production of cyclopentyl chloride - Google Patents
Production of cyclopentyl chlorideInfo
- Publication number
- JP2000136153A JP2000136153A JP10309676A JP30967698A JP2000136153A JP 2000136153 A JP2000136153 A JP 2000136153A JP 10309676 A JP10309676 A JP 10309676A JP 30967698 A JP30967698 A JP 30967698A JP 2000136153 A JP2000136153 A JP 2000136153A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- chloride
- hydrogen chloride
- cyclopentene
- carried out
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はシクロペンチルクロ
ライドの製造方法に関する。さらに詳しくは、シクロペ
ンテンと塩化水素との反応により、高収率でシクロペン
チルクロライドを製造する方法に関する。[0001] The present invention relates to a method for producing cyclopentyl chloride. More specifically, the present invention relates to a method for producing cyclopentyl chloride in high yield by reacting cyclopentene with hydrogen chloride.
【０００２】[0002]
【従来の技術】シクロペンチルクロライドは、医薬、農
薬または機能性高分子などの原料として有用である。ま
た溶剤、アルキル化剤あるいは有機金属化合物の製造に
も利用されている。2. Description of the Related Art Cyclopentyl chloride is useful as a raw material for pharmaceuticals, agricultural chemicals or functional polymers. It is also used for the production of solvents, alkylating agents or organometallic compounds.
【０００３】従来、脂環式オレフィンと塩化水素を反応
させて脂環式アルキルクロライドを製造する方法につい
ては、種々の触媒や溶媒が提案されている。例えば、特
開平３−３１２２８号公報によれば、脂環式アルキルク
ロライドの製造に触媒としてＡｌＣｌ3、ＦｅＣｌ3など
を使用し、溶媒として塩化メチレン、クロロホルムなど
を使用する方法が提案されている。しかしながら、上記
の方法では、触媒は後処理されなければならず、また溶
媒は分離回収する必要があるため、工程が煩雑となり工
業的に不利である。Conventionally, various catalysts and solvents have been proposed for producing alicyclic alkyl chlorides by reacting alicyclic olefins with hydrogen chloride. For example, JP-A-3-31228 proposes a method in which AlCl 3 , FeCl 3, or the like is used as a catalyst for the production of an alicyclic alkyl chloride, and methylene chloride, chloroform, or the like is used as a solvent. However, in the above method, the catalyst has to be post-treated, and the solvent has to be separated and recovered, which complicates the process and is industrially disadvantageous.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明者は、シ
クロペンテンと塩化水素との反応によるシクロペンチル
クロライドの製造において、前述した従来法における欠
点を改良し、工業的に有利で簡単なプロセスについて研
究を進めたところ、一定濃度の塩化水素水溶液中にて塩
化水素ガスを供給しながら或る温度条件下で反応する
と、特定の触媒や溶媒を使用しないでも高収率でシクロ
ペンチルクロライドが得られることが見出された。Accordingly, the present inventors have studied on an industrially advantageous and simple process in the production of cyclopentyl chloride by reacting cyclopentene with hydrogen chloride to improve the above-mentioned disadvantages in the conventional method. As a result, it was found that cyclopentyl chloride can be obtained in high yield without using a specific catalyst or solvent when the reaction is carried out under a certain temperature condition while supplying hydrogen chloride gas in an aqueous solution of hydrogen chloride at a certain concentration. Was issued.
【０００５】[0005]
【課題を解決するための手段】本発明は、かかる知見に
基づいて到達されたものであって、シクロペンテンと塩
化水素との反応によりシクロペンチルクロライドを製造
する方法において、該反応は、５０〜７０℃の温度にお
いてシクロペンテンおよび２５〜４０重量％の濃度を有
する塩化水素水溶液を含有する容器中にて、その容器に
ガス状塩化水素を吹き込みながら実施することを特徴と
するシクロペンチルクロライドの製造方法である。SUMMARY OF THE INVENTION The present invention has been achieved based on the above findings. In a method for producing cyclopentyl chloride by reacting cyclopentene with hydrogen chloride, the reaction is carried out at 50 to 70 ° C. A method for producing cyclopentyl chloride, characterized in that the method is carried out in a container containing cyclopentene and an aqueous solution of hydrogen chloride having a concentration of 25 to 40% by weight at a temperature of 2 to 3 while blowing gaseous hydrogen chloride into the container.
【０００６】以下、本発明方法についてさらに詳細に説
明する。本発明において、シクロペンテンと塩化水素と
の反応は、塩化水素の濃度が２５〜４０重量％、好まし
くは２８〜３８重量％の範囲の塩化水素水溶液中で行わ
れる。具体的には耐圧反応容器中に前記塩化水素水溶液
を入れ、次いでシクロペンテンをゆっくり添加して反応
を開始する。反応は５０〜７０℃の範囲、好ましくは５
０〜６５℃の範囲の温度で実施される。反応温度が前記
範囲よりも低いと、反応に時間がかかりまた収率も低下
する。一方前記範囲よりも高い温度では反応時間は短く
なるが、より耐圧性の反応容器が必要となり経済的に望
ましくない。Hereinafter, the method of the present invention will be described in more detail. In the present invention, the reaction between cyclopentene and hydrogen chloride is carried out in an aqueous hydrogen chloride solution having a hydrogen chloride concentration of 25 to 40% by weight, preferably 28 to 38% by weight. Specifically, the hydrogen chloride aqueous solution is put into a pressure-resistant reaction vessel, and then cyclopentene is slowly added to start the reaction. The reaction is in the range 50-70 ° C, preferably 5 ° C.
It is performed at a temperature in the range of 0-65 ° C. If the reaction temperature is lower than the above range, the reaction takes a long time and the yield decreases. On the other hand, if the temperature is higher than the above range, the reaction time becomes shorter, but a more pressure-resistant reaction vessel is required, which is not economically desirable.
【０００７】反応の経過とともに反応系中の塩化水素濃
度が低下し、反応がスムースに進行しなくなるのを防ぐ
ため、反応容器中にガス状塩化水素を吹き込みながら反
応を行う。このガス状塩化水素は連続的あるいは間歇的
に吹き込まれる。またガス状塩化水素は反応容器中の気
相部あるいは液相部のいずれかに吹き込んでもよい。ガ
ス状塩化水素の供給は、反応系内（液相部）の塩化水素
濃度が２５〜４０重量％の範囲に維持される割合で実施
される。In order to prevent the concentration of hydrogen chloride in the reaction system from decreasing with the progress of the reaction and prevent the reaction from proceeding smoothly, the reaction is carried out while blowing gaseous hydrogen chloride into the reaction vessel. This gaseous hydrogen chloride is blown in continuously or intermittently. The gaseous hydrogen chloride may be blown into either the gas phase or the liquid phase in the reaction vessel. The supply of gaseous hydrogen chloride is carried out at such a rate that the concentration of hydrogen chloride in the reaction system (liquid phase part) is maintained in the range of 25 to 40% by weight.
【０００８】本発明における反応は５０℃以上の温度で
実施されるのでシクロペンテンの液状を保持するため常
圧ないし加圧、具体的には常圧（１気圧）ないし３気圧
の範囲で行われる。望ましくは若干の加圧した条件下で
かつ密閉系で実施するのが有利である。また反応系にお
ける水の使用割合は、特に制限されないが、少ない量が
工業的に有利であり、シクロペンテンに対して重量で
０.１〜２倍の範囲が望ましい。Since the reaction in the present invention is carried out at a temperature of 50 ° C. or higher, the reaction is carried out at normal pressure or pressure, specifically, in the range of normal pressure (1 atm) to 3 atm to maintain the liquid state of cyclopentene. It is advantageous to work preferably under slightly pressurized conditions and in a closed system. The proportion of water used in the reaction system is not particularly limited, but a small amount is industrially advantageous, and is desirably 0.1 to 2 times the weight of cyclopentene.
【０００９】本発明は前記した条件下で実施することに
より、シクロペンテンの転化率が高くかつシクロペンチ
ルクロライドの選択率も高いので、極めて高い収率でシ
クロペンチルクロライドを得ることができる。従来知ら
れているように触媒を使用しないでも反応に効率的に進
行するので触媒は使用する必要もない。さらに水以外の
他の溶媒の使用は、何ら利点がなくその必要もない。When the present invention is carried out under the above-mentioned conditions, the conversion of cyclopentene is high and the selectivity of cyclopentyl chloride is high, so that cyclopentyl chloride can be obtained in an extremely high yield. It is not necessary to use a catalyst because the reaction proceeds efficiently without using a catalyst as conventionally known. Furthermore, the use of other solvents besides water has no advantage and is not necessary.
【００１０】本発明の反応終了後、反応混合物を冷却し
有機層（上層）を分離し、この有機層を簡単な蒸留操作
を実施することにより高純度のシクロペンチルクロライ
ドを単離することができる。After the completion of the reaction of the present invention, the reaction mixture is cooled to separate an organic layer (upper layer), and a high-purity cyclopentyl chloride can be isolated by performing a simple distillation operation on the organic layer.
【００１１】[0011]
【実施例】以下、実施例を掲げて本発明方法を説明す
る。 実施例１ ５００ｍｌガラス製耐圧容器に３６％濃塩酸１６０ｇを
仕込み密閉とし、撹拌下５０℃で２５０ｇのシクロペン
テンを１時間かけて添加した。次に、反応温度６５℃を
維持しつつ圧力２.０ｋｇ／ｃｍ2Ｇ以下で系内に塩化水
素ガス１３１ｇを６時間で導入し、さらに熟成反応を１
時間行った。反応終了後、２５℃まで冷却して有機層
（上層）を分離し、これに２％炭酸水素ナトリウム水溶
液２０ｇを加えて洗浄した後、無水硫酸マグネシウム５
ｇを添加して一夜放置した。この濾液を理論段数３段相
当の蒸留塔で蒸留したところ、無色透明液体で９９.９
％純度のシクロペンチルクロライド３７４.２ｇを得、
シクロペンテンはほとんど存在しなかった。これはシク
ロペンテンからワンパスの収率９７.５％であった。The method of the present invention will be described below with reference to examples. Example 1 A 500 ml glass pressure vessel was charged with 160 g of 36% concentrated hydrochloric acid and hermetically sealed, and 250 g of cyclopentene was added over 1 hour at 50 ° C. with stirring. Next, 131 g of hydrogen chloride gas was introduced into the system at a pressure of 2.0 kg / cm 2 G or less for 6 hours while maintaining the reaction temperature at 65 ° C., and the aging reaction was continued for 1 hour.
Time went. After completion of the reaction, the reaction mixture was cooled to 25 ° C., and the organic layer (upper layer) was separated. The organic layer was washed by adding 20 g of a 2% aqueous sodium hydrogen carbonate solution.
g was added and left overnight. This filtrate was distilled with a distillation column equivalent to three theoretical plates, and it was found to be 99.9 as a colorless transparent liquid.
374.2 g of cyclopentyl chloride with a purity of
Cyclopentene was almost absent. This gave a one-pass yield of 97.5% from cyclopentene.
【００１２】比較例１ ５００ｍｌガラス製耐圧容器に３６％濃塩酸１６０ｇを
仕込み密閉とし、撹拌下２０℃で２５０ｇのシクロペン
テンを１時間かけて添加した。次に、反応温度２０℃を
維持しつつ塩化水素ガス１３１ｇを３０時間で導入し
た。この間、圧力は最大９.７ｋｇ／ｃｍ2に達した。さ
らに熟成反応を１０時間行った。反応終了後、塩化水素
ガスをパージして圧力を常圧に戻した。そして有機層
（上層）を分離し、これに２％炭酸水素ナトリウム水溶
液１００ｇを加えて洗浄した後、無水硫酸マグネシウム
５ｇを添加して一夜放置した。この濾液を理論段数３段
相当の蒸留塔で蒸留したところ、９９.６％純度のシク
ロペンテン９４.３ｇを回収し、９９.５％純度のシクロ
ペンチルクロライド２１９.２ｇを得た。これはシクロ
ペンテンからワンパスの収率５７.１％であり、シクロ
ペンテンの回収を考慮すると収率９１.７％であった。Comparative Example 1 A 500 ml glass pressure vessel was charged with 160 g of 36% concentrated hydrochloric acid and sealed, and 250 g of cyclopentene was added over 1 hour at 20 ° C. with stirring. Next, 131 g of hydrogen chloride gas was introduced over 30 hours while maintaining the reaction temperature at 20 ° C. During this time, the pressure reached a maximum of 9.7 kg / cm 2 . Further, an aging reaction was performed for 10 hours. After completion of the reaction, the pressure was returned to normal pressure by purging hydrogen chloride gas. Then, the organic layer (upper layer) was separated, washed with 100 g of a 2% aqueous sodium hydrogencarbonate solution, added with 5 g of anhydrous magnesium sulfate, and allowed to stand overnight. The filtrate was distilled with a distillation column corresponding to three theoretical plates. As a result, 94.3 g of 99.6% pure cyclopentene was recovered to obtain 219.2 g of 99.5% pure cyclopentyl chloride. This was 57.1% in one pass from cyclopentene, and 91.7% in consideration of the recovery of cyclopentene.
【００１３】[0013]
【発明の効果】触媒や特殊な有機溶媒を使用することな
く、シクロペンテンの塩化水素による塩素化により、高
収率でシクロペンチルクロライドを製造することが可能
となる。According to the present invention, it is possible to produce cyclopentyl chloride in high yield by chlorinating cyclopentene with hydrogen chloride without using a catalyst or a special organic solvent.
Claims (4)
りシクロペンチルクロライドを製造する方法において、
該反応は、５０〜７０℃の温度においてシクロペンテン
および２５〜４０重量％の濃度を有する塩化水素水溶液
を含有する容器中にて、その容器にガス状塩化水素を吹
き込みながら実施することを特徴とするシクロペンチル
クロライドの製造方法。1. A process for producing cyclopentyl chloride by reacting cyclopentene with hydrogen chloride,
The reaction is carried out in a vessel containing cyclopentene and an aqueous solution of hydrogen chloride having a concentration of 25 to 40% by weight at a temperature of 50 to 70 ° C. while blowing gaseous hydrogen chloride into the vessel. A method for producing cyclopentyl chloride.
する請求項１記載の製造方法。2. The method according to claim 1, wherein the reaction is carried out in the substantial absence of a catalyst.
の範囲で実施する請求項１記載の製造方法。3. The method according to claim 1, wherein the reaction is carried out in a range from normal pressure (1 atm) to 3 atm.
で０.１〜２倍の水の存在下に実施する請求項１記載の
製造方法。4. The process according to claim 1, wherein the reaction is carried out in the presence of 0.1 to 2 times by weight of water relative to cyclopentene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10309676A JP2000136153A (en) | 1998-10-30 | 1998-10-30 | Production of cyclopentyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10309676A JP2000136153A (en) | 1998-10-30 | 1998-10-30 | Production of cyclopentyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000136153A true JP2000136153A (en) | 2000-05-16 |
Family
ID=17995941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10309676A Pending JP2000136153A (en) | 1998-10-30 | 1998-10-30 | Production of cyclopentyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000136153A (en) |
-
1998
- 1998-10-30 JP JP10309676A patent/JP2000136153A/en active Pending
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