JPS60224665A - Production of 1,4-substituted cyclohexane - Google Patents
Production of 1,4-substituted cyclohexaneInfo
- Publication number
- JPS60224665A JPS60224665A JP8114884A JP8114884A JPS60224665A JP S60224665 A JPS60224665 A JP S60224665A JP 8114884 A JP8114884 A JP 8114884A JP 8114884 A JP8114884 A JP 8114884A JP S60224665 A JPS60224665 A JP S60224665A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- urea
- reaction
- cyanocyclohexane
- carboxylic acid
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の目的）
本発明は、４−シアノシクロヘキサン−１−カルボン酸
の新規な製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Objects of the Invention) The present invention relates to a novel method for producing 4-cyanocyclohexane-1-carboxylic acid.
本発明の目的は止血剤等の医薬としてきわめて有効であ
るトランス−４−アミノメチルシクロヘキサン−１−カ
ルボン酸および抗潰瘍剤等として著効を示す塩酸セトウ
キサートの製造中間体である４−シアノシクロヘキサン
−１−カルボン酸を工業的にかつ高収率で製造すること
にある。The purpose of the present invention is to produce trans-4-aminomethylcyclohexane-1-carboxylic acid, which is extremely effective as a medicinal agent such as a hemostatic agent, and 4-cyanocyclohexane-1-carboxylic acid, which is an intermediate for producing cetoxate hydrochloride, which is highly effective as an anti-ulcer agent. An object of the present invention is to produce 1-carboxylic acid industrially and in high yield.
（従来の技術）
現在までに報告されている４−シアノシクロヘキサン−
１−カルボン酸の工業的製造法としては１）ヘキサハイ
ドロテレフタル酸またはこれと１．４−ジシアノシクロ
ヘキサンの混合物に温度２７０〜６４０℃でアンモニア
ガスを接触させる方法（特公昭４７−２３５３５）２）
ヘキサハイドロテレフタル酸とシクロヘキサン−１，４
−シカルボサミド／又はシクロヘキサン−１，４−ジカ
ルボニトリルとを２５０〜３５０℃の温度で加錫
熱する方法（特開／、４９−１１０６４９）が仰られて
いる。(Prior art) 4-cyanocyclohexane reported to date
Industrial methods for producing 1-carboxylic acid include 1) a method in which hexahydroterephthalic acid or a mixture of hexahydroterephthalic acid and 1,4-dicyanocyclohexane is brought into contact with ammonia gas at a temperature of 270 to 640°C (Japanese Patent Publication No. 47-23535); 2)
Hexahydroterephthalic acid and cyclohexane-1,4
- A method of heating cyclohexane-1,4-dicarbonitrile with tin at a temperature of 250 to 350° C. (Japanese Unexamined Patent Publication No. 49-110649) is mentioned.
（発明が解決しようとする問題点）
しかしながら、１）の方法は高圧ガスであるアンモニア
を高温で取扱わなければならない、又２）の方法は、１
，４−ゾカルボサミドをヘキサハイドロテレフタル酸よ
り誘導しなければならず、反応行程が長い欠点がある。(Problems to be solved by the invention) However, method 1) requires handling of ammonia, which is a high-pressure gas, at high temperatures;
, 4-zocarbosamide must be derived from hexahydroterephthalic acid, which has the disadvantage that the reaction process is long.
（２）発明の構成
（問題点を解決するための手段及び作用）本発明者らは
、上記の問題点を解決すべく、鋭意検討した結果、反応
に用いられるアンモニア供給源として、安価でかつ取扱
いの容易な尿素な用いること（よって、低廉かつ容易な
４−シアノシクロヘキサン−１−カルボン酸の新規なａ
ｎ方法を見い出した。(2) Structure of the Invention (Means and Effects for Solving the Problems) In order to solve the above problems, the inventors of the present invention have made extensive studies and found that an inexpensive and effective ammonia supply source for use in the reaction is available. The use of urea that is easy to handle (therefore, a novel a of 4-cyanocyclohexane-1-carboxylic acid that is inexpensive and easy
found a method.
以下に、本発明の実施方法を更に詳しく説明する。Below, the method of implementing the present invention will be explained in more detail.
反応は常圧下で行い、加熱温度は２３０〜３５０℃であ
る。反応温度が低いと反応速度が遅くなり、反応温度が
高いと６−アザビシクロ（ｉ２，２）ノナン−２，４−
ジオンのような反応副生物が生成が促進されるので２５
０〜３１０℃で行うのが望ましい。The reaction is carried out under normal pressure, and the heating temperature is 230 to 350°C. If the reaction temperature is low, the reaction rate will be slow, and if the reaction temperature is high, 6-azabicyclo(i2,2)nonane-2,4-
25 as the formation of reaction by-products such as diones is accelerated.
It is desirable to carry out at a temperature of 0 to 310°C.
尿素の使用量としては、反応原料であるヘキサハイドロ
テレフタル酸に対して０．５〜１０倍モル望ましくは２
〜５倍モルがよい。The amount of urea used is preferably 0.5 to 10 times the mole of hexahydroterephthalic acid, which is the reaction raw material.
~5 times the molar amount is preferable.
反応を促進するための反応触媒は特に用いなくてもよい
。特に反応速度を上昇する必要のある場合は、塩酸、硫
酸、リン酸などの鉱酸、又はアルミナ、五酸化リン、酸
化スズ、酸化鋼などの酸化物の使用が効果がある。触媒
の使用量は、ヘキサハイドロテレフタル酸に対して０．
５〜５ Ｑ ｗｔ％で行われるが、望ましくは０．５〜
５．０ ｗｔ％の範囲でよい。A reaction catalyst for promoting the reaction does not need to be used. Particularly when it is necessary to increase the reaction rate, it is effective to use mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or oxides such as alumina, phosphorus pentoxide, tin oxide, and oxidized steel. The amount of catalyst to be used is 0.0% relative to hexahydroterephthalic acid.
It is carried out at 5 to 5 Q wt%, but preferably 0.5 to 5
It may be in the range of 5.0 wt%.
未反応のヘキサハイドロテレフタル酸ト１．４ゾシアノ
シク口ヘキサンは抽出精製の操作すどにより回収した後
、本願発明の出発物質として再利用することができ、故
に原料を無駄な（目的物に変換することが可能である。Unreacted hexahydroterephthalate 1.4zocyanosic hexane can be recovered through extraction and purification operations and then reused as a starting material for the present invention, thus eliminating wasteful raw materials (converting them into target products). Is possible.
なお、上記のようＫして製造される４−シアノシクロヘ
キサン−１−カルボン酸は、例えハ、接触還元により４
−アミンメチルシクロヘキサン−１−カルメン酸に誘導
できる。In addition, 4-cyanocyclohexane-1-carboxylic acid produced by K as described above can be prepared by catalytic reduction.
-Aminemethylcyclohexane-1-carmenic acid.
（実施例）
実施例１
ヘキサハイドロテレフタル酸（シス：トランス比６２
： ３８ ） １７．２ 、Ｆ （０，１モル）、尿素
１５ｇ（０，２５モル）を混合し、１６０〜１６５℃で
４時間加熱する。その後加熱温度を２５０〜３１０℃に
上げ、２時間反応する。(Example) Example 1 Hexahydroterephthalic acid (cis:trans ratio 62
: 38) 17.2, F (0.1 mol) and 15 g (0.25 mol) of urea are mixed and heated at 160-165°C for 4 hours. After that, the heating temperature is raised to 250 to 310°C, and the reaction is carried out for 2 hours.
反応後、反応液をクロロホルム１００ｄＫ溶解し、５％
アンモニア水５０ゴで６回抽出する。クロロホルム層よ
す、シクロヘキサン−１，４−ジシアノシクロへキサ７
０．７９カー得られる。アンモニア水層を集め、１００
Ｍｔまで濃縮した後、塩酸でｐ）′１１．０〜２．０に
調整すれば、４−シアノシクロヘキサン−１−カルボン
酸１２．５ 、？ （０，０８２モル、収率８２チ）を
白色結晶として得ろ。本品をま示す。After the reaction, dissolve the reaction solution in chloroform at 100 dK and add 5%
Extract 6 times with 50 g of ammonia water. Chloroform layer, cyclohexane-1,4-dicyanocyclohexane 7
0.79 car is obtained. Collect the ammonia water layer, 100
After concentrating to Mt, if p)' is adjusted to 11.0 to 2.0 with hydrochloric acid, 4-cyanocyclohexane-1-carboxylic acid 12.5, ? (0,082 mol, yield 82 g) was obtained as white crystals. Show this product.
実施例２
ヘキサハイドロテレフタル酸１０３．２ ＆ （０，６
モル）、尿素７２．９（１，２モル）、酸イヒスズ１．
２１を混合し、２８０〜２９０℃で１時間反応する。Example 2 Hexahydroterephthalic acid 103.2 & (0,6
mol), urea 72.9 (1.2 mol), acid Ihistin 1.
21 and reacted at 280-290°C for 1 hour.
反応後、反応液にクロロホルム５００ｄを加え、酸化ス
ズを濾過によって除く。得られたクロロホルム溶液を５
チアンモニア水２００−で６回抽出する。アンモニア抽
出液を集め濃縮によって過第１のアンモニアを除去した
後、塩酸でｐＨ１，０〜２．０に調整すれば、４−シア
ノシクロヘキサン−１−カルボン酸８０．８１！（０，
５３モル、収率８８％）を得る。After the reaction, 500 d of chloroform is added to the reaction solution, and tin oxide is removed by filtration. The obtained chloroform solution was
Extract 6 times with 200ml of thiammonia water. After collecting the ammonia extracts and removing the primary ammonia by concentration, the pH was adjusted to 1.0 to 2.0 with hydrochloric acid to obtain 4-cyanocyclohexane-1-carboxylic acid of 80.81! (0,
53 mol, yield 88%).
（３１発明の効果
本発明によれば、ヘキサハイドロテレフタル酸を尿素と
２５０〜６１０°Ｃで加熱するｒイリで＠的とする４−
シアノシクロヘキサン−１−カルボン酸・しい（キて収
埼でさす。(31 Effects of the Invention According to the present invention, 4-
Cyanocyclohexane-1-carboxylic acid.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
で加熱することを特徴とする４−シアノシクロヘキサン
−１−カルボン酸の製造法Hexabitrotylental acid with urea at 250-310℃
A method for producing 4-cyanocyclohexane-1-carboxylic acid, characterized by heating with
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8114884A JPS60224665A (en) | 1984-04-24 | 1984-04-24 | Production of 1,4-substituted cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8114884A JPS60224665A (en) | 1984-04-24 | 1984-04-24 | Production of 1,4-substituted cyclohexane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60224665A true JPS60224665A (en) | 1985-11-09 |
Family
ID=13738341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8114884A Pending JPS60224665A (en) | 1984-04-24 | 1984-04-24 | Production of 1,4-substituted cyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60224665A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012046781A1 (en) * | 2010-10-07 | 2012-04-12 | 三井化学株式会社 | Method for producing bis(aminomethyl)cyclohexanes |
| CN103153940A (en) * | 2010-10-07 | 2013-06-12 | 三井化学株式会社 | Method for producing trans-1,4-bis(aminomethyl)cyclohexane |
-
1984
- 1984-04-24 JP JP8114884A patent/JPS60224665A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012046781A1 (en) * | 2010-10-07 | 2012-04-12 | 三井化学株式会社 | Method for producing bis(aminomethyl)cyclohexanes |
| CN103153940A (en) * | 2010-10-07 | 2013-06-12 | 三井化学株式会社 | Method for producing trans-1,4-bis(aminomethyl)cyclohexane |
| US8865938B2 (en) | 2010-10-07 | 2014-10-21 | Mitsui Chemicals, Inc. | Method for producing bis(aminomethyl)cyclohexanes |
| US8865939B2 (en) | 2010-10-07 | 2014-10-21 | Mitsui Chemicals, Inc. | Method for producing trans-1,4-bis(aminomethyl) cyclohexane |
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