JPS605573B2 - Method for producing exo-trimethylene norbornane - Google Patents
Method for producing exo-trimethylene norbornaneInfo
- Publication number
- JPS605573B2 JPS605573B2 JP56117067A JP11706781A JPS605573B2 JP S605573 B2 JPS605573 B2 JP S605573B2 JP 56117067 A JP56117067 A JP 56117067A JP 11706781 A JP11706781 A JP 11706781A JP S605573 B2 JPS605573 B2 JP S605573B2
- Authority
- JP
- Japan
- Prior art keywords
- tmn
- exo
- endo
- reaction
- friedel
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】
本発明はェキソートリメチレンノルボルナン（以下、ェ
キソ−ＴＭＮと略す。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to exotrimethylene norbornane (hereinafter abbreviated as exo-TMN).
）の製造方法に関する。エンドートリメチレンノルボル
ナン（以下、エンド−ＴＭＮと略す。). Endo trimethylene norbornane (hereinafter abbreviated as endo-TMN).
）をェキソーＴＭＮに異性化する反応の触媒として、硫
酸や塩化アルミニウムが知られている。しかし、硫酸は
ェキソ−ＴＭＮへの転化速度が遅く「 しかも収率も高
くないという欠点がある。また、塩化アルミニウムなど
は酸強度が大であるため、反応がェキソーＴＭＮにとど
まらずアダマンタンにまで進行してしまい、ェキソ−Ｔ
ＭＮを選択的に得ることは困難である。このような欠点
を改良するため、アルミナに担持された金属パラジウム
触媒を用いる方法（特公昭５１−３６７４８号公報）、
ゼオラィトなどの固体触媒を用いる方法（特開昭５５−
７２１２２号公報）などがあるが、反応温度や圧力が比
較的高く、かつ収率も十分でない欠点がある。さらに、
フリーデル・クラフト型触媒の存在下、芳香族溶媒中で
異性化を行なう方法も提案されている（特公昭５２一４
６２２４号公報）が、この方法では原料のエンド−ＴＭ
Ｍこ対し２０重量％以上という過剰の触媒を使用する必
要があり、後処理工程が複雑になると共に、反応時間や
収率も十分ではなかった。本発明は目的は上記のような
欠点を解消したェキソ−ＴＭＮの効率的な製造方法を提
供することである。Sulfuric acid and aluminum chloride are known as catalysts for the isomerization reaction of ) to Exo TMN. However, sulfuric acid has the disadvantage that the conversion rate to exo-TMN is slow and the yield is not high. Also, since aluminum chloride has a high acid strength, the reaction progresses not only to exo-TMN but also to adamantane. I ended up using Exo-T.
It is difficult to obtain MN selectively. In order to improve these drawbacks, a method using a metal palladium catalyst supported on alumina (Japanese Patent Publication No. 51-36748),
A method using a solid catalyst such as zeolite (Japanese Patent Application Laid-Open No. 1983-
No. 72122), but the drawbacks are that the reaction temperature and pressure are relatively high and the yield is not sufficient. moreover,
A method of isomerization in an aromatic solvent in the presence of a Friedel-Crafts type catalyst has also been proposed (Japanese Patent Publication No. 52-14
6224), but in this method, the raw material Endo-TM
It was necessary to use an excess catalyst of 20% by weight or more based on M, which made the post-treatment process complicated, and the reaction time and yield were not sufficient. An object of the present invention is to provide an efficient method for producing Exo-TMN that eliminates the above-mentioned drawbacks.
本発明は、エンド−ＴＭＮをフリーデル・クラフト型触
媒の存在下に異性化するに際し、溶媒として炭素数１〜
４個のジハロゲン化炭化水素を用い、フリーデル・クラ
フト型触媒をエンド一ＴＭＮの重量に基いて１〜２０％
の範囲で用いることを特徴とするェキソーＴＭＮの製造
方法である。In the present invention, when endo-TMN is isomerized in the presence of a Friedel-Crafts type catalyst, the solvent has 1 to 1 carbon atoms.
Using four dihalogenated hydrocarbons, the Friedel-Crafts type catalyst is 1 to 20% based on the weight of the endo-TMN.
This is a method for producing Exo TMN, which is characterized in that it is used within the following range.
エンド−ＴＭＮをェキソーＴＭＮ‘こ異性化する反応は
次式で表わされる。The reaction for isomerizing endo-TMN into exo-TMN' is represented by the following formula.
上記反応に用いるフリーデル・クラフト型触媒としては
塩化アルミニウム、臭化アルミニウム、塩化鉄、塩化す
ず、塩化チタンなどがあり、これらの中では塩化アルミ
ニウムが好ましい。Examples of the Friedel-Crafts type catalyst used in the above reaction include aluminum chloride, aluminum bromide, iron chloride, tin chloride, and titanium chloride, and among these, aluminum chloride is preferred.
この触媒は原料であるエンド−ＴＭＮの重量に塞いて１
〜２０％、好ましくは２〜１０％の割合で使用する。こ
のように、本発明によれば触媒使用量は従釆法よりも少
なくてすむが、その理由は後記する特定の溶媒と組合せ
て用いることにある。本発明の方法では溶媒としてジハ
ロゲン化炭化水素を用いるが、その具体例として塩化メ
チレン、臭化メチレン「１１２−ジクロルヱタン「１・
２−ジクロルプロ／ゞン、１・３−ジクロルプロパン、
１・４−ジクロルプタンなどを挙げることができる。This catalyst has a weight of 1
It is used in a proportion of ~20%, preferably 2-10%. As described above, according to the present invention, the amount of catalyst used can be smaller than that of the secondary method, and the reason for this is that it is used in combination with a specific solvent to be described later. In the method of the present invention, a dihalogenated hydrocarbon is used as a solvent, and specific examples thereof include methylene chloride, methylene bromide, "112-dichloroethane"
2-dichloropropane, 1,3-dichloropropane,
Examples include 1,4-dichlorobutane.
この場合の炭化水素としては炭素数４個程度までのもの
が好ましい。溶媒の使用量については特に制限はないが
、通常はエンド−ＴＭＮ使用量の２〜５倍程度を目安と
して用いる。反応温度は０〜１００００、好ましくは１
５〜８００○であり、また反応時間については反応温度
など他の条件により異なるが、通常は０．５〜５時間で
ある。In this case, the hydrocarbon preferably has up to about 4 carbon atoms. There is no particular restriction on the amount of solvent used, but it is usually about 2 to 5 times the amount of endo-TMN used. The reaction temperature is 0 to 10,000, preferably 1
The reaction time varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 5 hours.
反応温度が１００００よりも高くなると、タールの生成
がみられるので好ましくない。本発明によれば、高純度
のェキソーＴＭＮを高い収率で得ることができる。When the reaction temperature is higher than 10,000, tar is generated, which is not preferable. According to the present invention, highly pure Exo TMN can be obtained in high yield.
すなわち、ェキソ−ＴＭＮの純度は９７％以上であり、
その収率は一般的に９５〜１００％である。エンド−Ｔ
ＭＮや結晶性アダマンタンが共存する場合、これらの混
合物からェキソ−ＴＭＮを精製することは非常に困難で
あることを考慮すると、上記の如く高純度でェキソ−Ｔ
ＭＮを得る本発明の方法は実用性に富み、かつ特殊燃料
としての利用などのェキソ−ＴＭＮの用途も拡大される
。また、本発明の方法は触媒の使用量が少ないため、後
処理が簡便であるほか、反応を比較的低温、低圧で行な
えるので設備やエネルギーコストが低いという特色があ
る。That is, the purity of Exo-TMN is 97% or more,
The yield is generally 95-100%. End-T
Considering that it is very difficult to purify exo-TMN from a mixture of these when MN and crystalline adamantane coexist, exo-TMN can be purified with high purity as described above.
The method of the present invention for obtaining MN is highly practical and expands the applications of exo-TMN, such as its use as a special fuel. Furthermore, since the method of the present invention uses a small amount of catalyst, post-treatment is simple, and since the reaction can be carried out at relatively low temperature and low pressure, equipment and energy costs are low.
さらに、反応時間が短かし、のでタールの生成量が少な
いことも本発明の利点の１つである。本発明によって得
られるヱキソ−ＴＭＮはロケット燃料、ジェット燃料な
どとして用いられるほか、各種燃料、潤滑剤への添加剤
、有機合成中間体、溶剤等としての利用も期待される。Furthermore, one of the advantages of the present invention is that the reaction time is short and therefore the amount of tar produced is small. Exo-TMN obtained by the present invention can be used as rocket fuel, jet fuel, etc., and is also expected to be used as various fuels, additives for lubricants, organic synthesis intermediates, solvents, etc.
次に、本発明を実施例によって説明する。Next, the present invention will be explained by examples.
実施例
塩化アルミニウム５夕をフラスコ中の１・２ージクロル
ェタン１００泌に縄拝しながら加えた。EXAMPLE 5 portions of aluminum chloride were added to 100 portions of 1,2-dichloroethane in a flask while stirring.
一方、別にエンド−ＴＭＮＩＯＯ夕を１・２−ジクロル
ェタン２００泌に溶解させたものを予め調製しておき、
この溶液を滴下ロートを用いて前記フラスコ中に室温で
燈拝しながら約１時間かけてゆっくり滴下した。その後
、３５〜４０００で３び分間反応を続けた。反応終了後
、冷水を添加して塩化アルミニウムを分解し、静遣した
後、油層を分離して水洗した。On the other hand, separately prepare in advance a solution of endo-TMNIOO dissolved in 200 g of 1,2-dichloroethane,
This solution was slowly added dropwise into the flask using a dropping funnel over a period of about 1 hour at room temperature. Thereafter, the reaction was continued for 3 minutes at 35-4000 ℃. After the reaction was completed, cold water was added to decompose the aluminum chloride, and after the mixture was allowed to stand still, the oil layer was separated and washed with water.
次いで、脱水後１・２−ジクロルェタンを留去した。反
応生成物をガスクロマトグラフィ一で分析したところ、
転化率はほぼ１００％、選択率は９６％でヱキソ−ＴＭ
Ｎが得られたことが判った。Then, after dehydration, 1,2-dichloroethane was distilled off. When the reaction products were analyzed by gas chromatography,
The conversion rate was almost 100% and the selectivity was 96%.
It turned out that N was obtained.
なお、副生物は０．８％のアダマンタンと竪質分であり
、タールの生成はほとんどみられなかった。参考例
塩化アルミニウム１０のこｔ−ブチルクロライド１．５
夕を加えてて３０分反応させた。The by-products were 0.8% adamantane and vertices, and almost no tar was observed. Reference example Aluminum chloride 10% t-Butyl chloride 1.5
I added water and let it react for 30 minutes.
これにエンド−ＴＭＮ５０夕をトルェン１００の【に熔
解させたものを加えた。室温で３時間反応させたときの
ェキソーＴＭＮの収率は８２％であった。To this was added 50% Endo-TMN dissolved in 100% toluene. The yield of Exo TMN was 82% when reacted at room temperature for 3 hours.
Claims (1)
クラフト型触媒の存在下に異性化するに際し、溶媒とし
て炭素数１〜４個のジハロゲン化炭化水素を用い、フリ
ーデル・クラフト型触媒をエンド−トリメチレンノルボ
ルナンの重量に基いて１〜２０％の範囲で用いることを
特徴とするエキソ−トリメチレンノルボルナンの製造方
法。 ２ フリーデル・クラフト型触媒が塩化アルミニウムで
ある特許請求の範囲第１項記載の方法。 ３ ジハロゲン化炭化水素が１・２−ジクロルエタンで
ある特許請求の範囲第１項記載の方法。[Claims] 1. Endo-trimethylene norbornane is prepared by Friedel
In the isomerization in the presence of a Kraft-type catalyst, a dihalogenated hydrocarbon having 1 to 4 carbon atoms is used as the solvent, and a Friedel-Crafts-type catalyst is used in an amount of 1 to 20% based on the weight of endo-trimethylenenorbornane. A method for producing exo-trimethylenenorbornane, characterized in that it is used in a range of 2. The method according to claim 1, wherein the Friedel-Crafts type catalyst is aluminum chloride. 3. The method according to claim 1, wherein the dihalogenated hydrocarbon is 1,2-dichloroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56117067A JPS605573B2 (en) | 1981-07-28 | 1981-07-28 | Method for producing exo-trimethylene norbornane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56117067A JPS605573B2 (en) | 1981-07-28 | 1981-07-28 | Method for producing exo-trimethylene norbornane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5818324A JPS5818324A (en) | 1983-02-02 |
| JPS605573B2 true JPS605573B2 (en) | 1985-02-12 |
Family
ID=14702598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56117067A Expired JPS605573B2 (en) | 1981-07-28 | 1981-07-28 | Method for producing exo-trimethylene norbornane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS605573B2 (en) |
-
1981
- 1981-07-28 JP JP56117067A patent/JPS605573B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5818324A (en) | 1983-02-02 |
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