JP2003286257A - Method for producing 3-aminopropyl derivative - Google Patents
Method for producing 3-aminopropyl derivativeInfo
- Publication number
- JP2003286257A JP2003286257A JP2003015496A JP2003015496A JP2003286257A JP 2003286257 A JP2003286257 A JP 2003286257A JP 2003015496 A JP2003015496 A JP 2003015496A JP 2003015496 A JP2003015496 A JP 2003015496A JP 2003286257 A JP2003286257 A JP 2003286257A
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- derivative
- aminopropyl
- cyanoethyl
- catalyst
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脱ハロゲン化水素
剤や重合反応の触媒として有用な１，８−ジアザビシク
ロ［５．４．０］−７−ウンデセン、又は、１，５−ジ
アザビシクロ［４．３．０］−５−ノネン等を製造する
際の重要中間体である３−アミノプロピル誘導体の製造
法に関する。TECHNICAL FIELD The present invention relates to 1,8-diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4] useful as a dehydrohalogenating agent or a catalyst for polymerization reaction. .3.0] -5-Nonene and the like, the present invention relates to a method for producing a 3-aminopropyl derivative which is an important intermediate.
【０００２】[0002]
【従来の技術】セバコニトリルからラネーニッケル触媒
を用いてエタノールと液体アンモニアに溶解し、水素添
加し、デカメチレンジアミンを得る方法及びベンジルニ
トリルから同様にラネーニッケル触媒を用いて液体アン
モニアに溶解し、水素添加し、β−フェニルエチルアミ
ンを得る方法が記載されている（非特許文献１参照）。2. Description of the Related Art A method of obtaining decamethylenediamine by dissolving hydrogen from sevaconitrile using Raney nickel catalyst in ethanol and liquid ammonia, and a method of dissolving benzylnitrile in liquid ammonia using Raney nickel catalyst in the same manner and hydrogenating , Β-phenylethylamine have been described (see Non-Patent Document 1).
【０００３】又、１−（２−シアノエチル）−ε−カプ
ロラクタムをメタノールと液体アンモニアに溶解し、ラ
ネーニッケル触媒を用いて、水素添加し、１−（３−ア
ミノプロピル）−ε−カプロラクタムを得る方法が記載
されている（特許文献１参照）。Further, 1- (2-cyanoethyl) -ε-caprolactam is dissolved in methanol and liquid ammonia and hydrogenated using Raney nickel catalyst to obtain 1- (3-aminopropyl) -ε-caprolactam. Is described (see Patent Document 1).
【０００４】いずれの場合もラネーニッケル触媒と液体
アンモニアを用いているが、ラネーニッケル触媒は、発
火性が強く、また、液体アンモニアは特有の不快臭があ
り、且つ毒性面でも問題があって作業環境上好ましくな
い。In both cases, Raney nickel catalyst and liquid ammonia are used, but Raney nickel catalyst has a strong ignitability, liquid ammonia has a peculiar unpleasant odor, and there is a problem in terms of toxicity. Not preferable.
【０００５】[0005]
【特許文献１】特公昭４５−４１２２６号公報[Patent Document 1] Japanese Patent Publication No. 45-41226
【非特許文献１】Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ
Ｃｏｌｌｅｃｔｉｖｅ Ｖｏｌｕｍｅ第３巻、２２９
頁及び７２０頁[Non-Patent Document 1] Organic Syntheses
Collective Volume Volume 3, 229
Pages and pages 720
【０００６】[0006]
【発明が解決しようとする課題】ラネーニッケル触媒を
用いて２−シアノエチル誘導体を、３−アミノプロピル
誘導体に変換する反応は、ラネーニッケル触媒の発火性
が強いことと、悪臭物質であり、劇物である液体アンモ
ニアを用いているため、作業環境上発火性が弱く、アン
モニアを使用せずに収率良く還元できる触媒が望まれて
いた。The reaction for converting a 2-cyanoethyl derivative into a 3-aminopropyl derivative using a Raney nickel catalyst is a strong ignitability of the Raney nickel catalyst, and is a foul-smelling substance and a deleterious substance. Since liquid ammonia is used, its ignitability is weak in the working environment, and a catalyst that can be reduced in good yield without using ammonia has been desired.
【０００７】更に煩雑な操作を経ず触媒を繰り返し使用
しても収率が低下しない触媒が望まれていた。There has been a demand for a catalyst that does not reduce the yield even if the catalyst is repeatedly used without complicated operations.
【０００８】本発明者らは、上記課題を解決すべく鋭意
検討した結果、２−シアノエチル誘導体をラネーコバル
ト触媒の存在下、水素添加することにより、３−アミノ
プロピル誘導体を製造できること、及び、上記反応の
際、ラネーコバルト触媒を繰り返し使用することが出来
ることを見出し、本発明を完成した。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a 3-aminopropyl derivative can be produced by hydrogenating a 2-cyanoethyl derivative in the presence of a Raney cobalt catalyst. The present invention was completed by finding that the Raney cobalt catalyst can be repeatedly used during the reaction.
【０００９】[0009]
【課題を解決するための手段】本発明は、一般式（I）
を有する２−シアノエチル誘導体（式中、ｎは１乃至４
を示す。）を、ラネーコバルトの存在下、水素添加する
ことよる一般式（II）を有する３−アミノプロピル誘導
体（式中、ｎは１乃至４を示す。）の製造法である。The present invention has the general formula (I)
A 2-cyanoethyl derivative having: (wherein n is 1 to 4)
Indicates. Is hydrogenated in the presence of Raney cobalt to produce a 3-aminopropyl derivative having the general formula (II) (wherein n is 1 to 4).
【００１０】[0010]
【化２】 [Chemical 2]
【００１１】また、本発明は、上記反応において、ラネ
ーコバルトを繰り返し使用する製造法である。The present invention is also a production method in which Raney cobalt is repeatedly used in the above reaction.
【００１２】本発明に使用される２−シアノエチル誘導
体としては、好適には１−（２−シアノエチル）―ε―
カプロラクタム（ｎ＝３）、又は、１−（２−シアノエ
チル）−２−ピロリドン（ｎ＝１）が挙げられ、更に好
適には１−（２−シアノエチル）−ε−カプロラクタム
（ｎ＝３）があげられる。The 2-cyanoethyl derivative used in the present invention is preferably 1- (2-cyanoethyl) -ε-
Caprolactam (n = 3) or 1- (2-cyanoethyl) -2-pyrrolidone (n = 1) can be mentioned, more preferably 1- (2-cyanoethyl) -ε-caprolactam (n = 3). can give.
【００１３】２−シアノエチル誘導体の還元工程で使用
されるラネーコバルトは、２−シアノエチル誘導体に対
し、重量比率で好適には０．０５乃至１０％であり、更
に好適には０．３乃至５％である。The Raney cobalt used in the step of reducing the 2-cyanoethyl derivative is preferably 0.05 to 10% by weight, more preferably 0.3 to 5%, based on the weight of the 2-cyanoethyl derivative. Is.
【００１４】ラネーコバルトを、繰り返し使用しても水
素吸収の速度に変化は見られず、収率を低下させること
なく３−アミノプロピル誘導体を繰り返し製造できる。Even if Raney cobalt is repeatedly used, the rate of hydrogen absorption does not change, and the 3-aminopropyl derivative can be repeatedly produced without lowering the yield.
【００１５】[0015]
【発明の実施の形態】本発明は、ラネ-コバルトの存在
下、２−シアノエチル誘導体を還元し、３−アミノプロ
ピル誘導体を製造する。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a 2-cyanoethyl derivative is reduced in the presence of Raney-cobalt to produce a 3-aminopropyl derivative.
【００１６】ラネーコバルトは日揮化学（株）等から入
手することが出来る。Raney cobalt can be obtained from JGC Corporation.
【００１７】本発明は、溶媒の存在下又は非存在下行な
われるが、好適には、溶媒の存在下行なう。使用する溶
媒は、例えば炭素数１乃至６のアルコールが挙げられ
る。これらのアルコールとしては、例えばメタノール、
エタノール、プロパノール、イソプロパノール、又は、
ブタノールが挙げられ、好適にはメタノール、エタノー
ル、又は、イソプロパノールが挙げられ、更に好適には
エタノール、又は、イソプロパノールが挙げられる。The present invention is carried out in the presence or absence of a solvent, preferably in the presence of a solvent. Examples of the solvent used include alcohols having 1 to 6 carbon atoms. Examples of these alcohols include methanol,
Ethanol, propanol, isopropanol, or
Butanol is used, preferably methanol, ethanol, or isopropanol is used, and more preferably, ethanol or isopropanol is used.
【００１８】反応時間は、温度、圧力、又は、触媒量に
より異なるが、通常１時間乃至２４時間であり、好適に
は１時間乃至１２時間である。The reaction time varies depending on the temperature, the pressure, or the amount of catalyst, but is usually 1 hour to 24 hours, and preferably 1 hour to 12 hours.
【００１９】反応温度は、圧力や触媒量によって異なる
が、通常室温乃至２５０℃であり、好適には５０乃至２
００℃であり、特に好適には８０乃至１５０℃である。The reaction temperature varies depending on the pressure and the amount of catalyst, but is usually room temperature to 250 ° C., preferably 50 to 2
The temperature is 00 ° C, particularly preferably 80 to 150 ° C.
【００２０】水素添加の際の、水素による加圧の圧力
は、１０乃至６０ｋｇ／ｃｍ2であり、好適には水素で
３０乃至６０ｋｇ／ｃｍ2であり、更に好適には３０乃
至５０ｋｇ／ｃｍ2である。The pressure applied by hydrogen during hydrogenation is 10 to 60 kg / cm 2 , preferably 30 to 60 kg / cm 2 with hydrogen, and more preferably 30 to 50 kg / cm 2. Is.
【００２１】計算量に近い水素が吸収された後、冷却、
静置し、下部に沈んだ触媒層と溶媒層を分離し、溶媒層
を濾過し、溶剤を留去し、３−アミノプロピル誘導体を
得る。After the calculated amount of hydrogen is absorbed, cooling is performed.
The mixture is left to stand, the catalyst layer and the solvent layer that have sunk in the lower part are separated, the solvent layer is filtered, and the solvent is distilled off to obtain a 3-aminopropyl derivative.
【００２２】得られた３−アミノプロピル誘導体は、そ
のまま次の工程に用いても良く、減圧蒸留により精製し
ても良い。The obtained 3-aminopropyl derivative may be used as it is in the next step, or may be purified by distillation under reduced pressure.
【００２３】更に下部に沈んだ触媒層に、新たに２−シ
アノエチル誘導体を加え、同様な反応、処理及び蒸留を
行い３−アミノプロピル誘導体を製造することが出来
る。The 2-aminoethyl derivative can be newly added to the catalyst layer that has sunk in the lower portion, and the same reaction, treatment and distillation can be carried out to produce a 3-aminopropyl derivative.
【００２４】本発明の原料である一般式（Ｉ）を有する
２−シアノエチル誘導体は、Ｒ．Ｅ．Ｂｅｎｓｏｎ等、
Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，第７０巻，２１１５
頁（１９４８年）や特公昭４５−４１２２６号公報等記
載の方法により、環状ラクタムとアクリロニトリルを反
応させ容易に合成される。例えば１−（２−シアノエチ
ル）−ε−カプロラクタムはε−カプロラクタムとアク
リロニトリルをイソプロパノール中触媒量の水酸化カリ
を用いて７０乃至９０℃で反応させて合成する。反応
後、塩酸または希硫酸で中和し、必要に応じて、蒸留に
よって精製する。The 2-cyanoethyl derivative having the general formula (I), which is a raw material of the present invention, is described in E. Benson et al.
J. Am. Chem. Soc. , Volume 70, 2115
It is easily synthesized by reacting a cyclic lactam with acrylonitrile according to the method described on page (1948) and Japanese Patent Publication No. 45-41226. For example, 1- (2-cyanoethyl)-[epsilon] -caprolactam is synthesized by reacting [epsilon] -caprolactam with acrylonitrile at 70 to 90 [deg.] C. using a catalytic amount of potassium hydroxide in isopropanol. After the reaction, the mixture is neutralized with hydrochloric acid or diluted sulfuric acid, and if necessary, purified by distillation.
【００２５】また、本発明により製造された３−アミノ
プロピル誘導体を水と共沸混合する有機溶剤、例えば、
キシレン、トルエン等と加熱し、生成する水を系外に除
去することによる分子内脱水・環化によりビシクロ誘導
体が得られる。Further, an organic solvent for azeotropically mixing the 3-aminopropyl derivative produced by the present invention with water, for example,
The bicyclo derivative is obtained by intramolecular dehydration / cyclization by heating with xylene, toluene or the like and removing the produced water out of the system.
【００２６】このようにして得られた、ビシクロ誘導
体、例えば１，８−ジアザビシクロ［５．４．０］−７
−ウンデセン及び１，５−ジアザビシクロ［４．３．
０］−５−ノネンはいずれも強塩基性で脱ハロゲン化剤
として有用であり、特に１，８−ジアザビシクロ［５．
４．０］−７−ウンデセンはウレタン硬化触媒としても
有用である。The bicyclo derivative thus obtained, for example, 1,8-diazabicyclo [5.4.0] -7.
-Undecene and 1,5-diazabicyclo [4.3.
0] -5-nonene is strongly basic and is useful as a dehalogenating agent, and particularly 1,8-diazabicyclo [5.
4.0] -7-Undecene is also useful as a urethane curing catalyst.
【００２７】[0027]
【実施例】以下、実施例等をあげて説明するが、本発明
はこれらにより制限されるものではない。（製造例１）１−（２−シアノエチル）−ε−カプロラ
クタムの合成
ε―カプロラクタム２５０ｇをイソプロパノール１２５
ｇに溶解し、水酸化カリウム０．５ｇを加え、撹拌しな
がらアクリロニトリル１５２ｇを７０乃至８０℃で２時
間かけて滴下した。滴下収量後さらに８０乃至９０℃で
２時間反応を継続し、１−（２−シアノエチル）−ε−
カプロラクタム反応液５２７ｇを得た。この反応を繰り
返し行ない、得られた反応液を、そのまま実施例１およ
び実施例２に示す１−（３−アミノプロピル）−ε−カ
プロラクタムの合成に使用した。尚、一部の反応液を２
０％硫酸で中和後減圧下に蒸留して、１５６乃至１６１
℃／３ｍｍＨｇで純度９４％の１−（２−シアノエチ
ル）−ε−カプロラクタムを得た。（製造例２）１−（２−シアノエチル）−２−ピロリド
ンの合成
２−ピロリドン２５０ｇをイソプロパノール１２５ｇに
溶解し、水酸化カリウム０．５ｇを加え、撹拌しながら
アクリロニトリル２０３ｇを７０−７５℃で１時間かけ
て滴下した。滴下収量後さらに８０−８５℃で２時間反
応を継続し、１−（２−シアノエチル）−２−ピロリド
ン反応液５７６ｇを得た。このものを、そのまま実施例
３に示す１−（３−アミノプロピル）−２−ピロリドン
の合成に使用した。（実施例１）１−（３−アミノプロピル）−ε−カプロ
ラクタムの合成
攪拌機、温度計、水素導入管を備えたオートクレーブ
に、製造例１より得た１−（２−シアノエチル）−ε−
カプロラクタム反応液４６２ｇおよびラネーコバルト触
媒（日揮化学（株） Ｎ−３５４Ｄ）１２ｇ（純分）を
入れ、温度１２５−１３５℃、３５−４０ｋｇ／ｃｍ2
水素加圧下で水素添加した。計算量に近い水素が吸収さ
れた後、冷却、静置し、下部に沈んだ触媒層と溶媒層を
分離し、溶媒層４５６ｇを得た。これをガスクロマトグ
ラフで分析したところ、未反応原料は検出さず、目的物
の純度は８６％（溶媒を除く）であった。このものを、
濾過後溶剤を留去して参考例３に示す１，８−ジアザビ
シクロ［５．４．０］−７−ウンデセンの合成に使用し
た。尚、別に同様の反応を行ない、得られた反応液を減
圧下に蒸留して、１４０−１４１℃／３ｍｍＨｇで純度
９７％の１−（３−アミノプロピル）−ε−カプロラク
タムを得た。
赤外吸収スペクトル νｃｍ-1（ｎｅａｔ）：２９２
８．２，２８５８．７，１６３３．４，１４８６．０，
１４４４．９，１４２５．１，１３５２．５，１１９
８．５，１０８２．５，９７５．８.
核磁気共鳴スペクトル（４００ＭＨｚ，ＣＤＣｌ3）δ
ｐｐｍ：１．５７〜１．７６（８Ｈ，ｍ），２．５１〜
２．５４（２Ｈ，ｍ），２．６９（２Ｈ，ｔ，Ｊ＝６．
６Ｈｚ），３．３２〜３．３４（２Ｈ，ｍ），３．４６
（２Ｈ，ｔ，Ｊ＝６．９Ｈｚ），７．２７（２Ｈ，
ｓ）.（実施例２）触媒の連続使用による１−（３−アミノプ
ロピル）−ε−カプロラクタムの合成
実施例１より得た下部に沈んだ触媒層と、製造例１より
得た１−（２−シアノエチル）−ε−カプロラクタム反
応液４６９ｇを実施例１と同様に反応、処理し、溶媒層
４６９ｇを得た。これをガスクロマトグラフで分析した
ところ、未反応原料は検出さず、目的物の純度は８９％
（溶媒を除く）であった。この反応を合計５回繰り返し
た時の収率及び純度等の結果を表１に示す。
表１
1サイクル ２サイクル ３サイクル ４サイクル ５サイクル
溶媒層収率 ９９％ １００％ ９９％ １００％ １００％
GC純度 ８６％ ８９％ ８８％ ８９％ ８５％ 未反応原料 検出せず 検出せず 検出せず 検出せず 検出せず （実施例３）１−（３−アミノプロピル）−２−ピロリ
ドンの合成
攪拌機、温度計、水素導入管を備えたオートクレーブ
に、製造例２より得た１−（２−シアノエチル）−２−
ピロリドン反応液５００ｇおよびラネーコバルト触媒
（日揮化学（株） Ｎ−３５４Ｄ）１０．９ｇ（純分）
を入れ、温度１２５−１３５℃、３５−４０ｋｇ／ｃｍ
2水素加圧下で水素添加した。計算量に近い水素が吸収
された後、冷却、静置し、下部に沈んだ触媒層と溶媒層
を分離し、溶媒層５００ｇを得た。これをガスクロマト
グラフで分析したところ、未反応原料は検出さず、目的
物の純度は９８％（溶媒を除く）であった。また、溶媒
層を濾過し、溶剤を留去し、減圧下に蒸留して、１２１
−１２３℃／４ｍｍＨｇで純度９８％の１−（３−アミ
ノプロピル）−２−ピロリドンを得た。（参考例１）１，８−ジアザビシクロ［５．４．０］−
７−ウンデセンの合成
実施例１より得た１−（３−アミノプロピル）−ε−カ
プロラクタム反応液の溶媒層４５６ｇを濾過後、溶媒を
留去し、これにキシレン１６９ｇとｐ−トルエンスルホ
ン酸一水塩４．５ｇを加えて１４５−１６５℃で１３時
間還流脱水した。得られた反応混合物を５０％水酸化ナ
トリウム１．５ｇで中和後減圧下に蒸留して、１３３−
１３７℃／２０ｍｍＨｇで純度９９％の１，８−ジアザ
ビシクロ［５．４．０］−７−ウンデセン２３３ｇを得
た。得られた１，８−ジアザビシクロ［５．４．０］−
７−ウンデセンは、東京化成工業（株）製の製品と、赤
外吸収スペクトル及びガスクロマトグラフの保持時間は
一致した。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. (Production Example 1) 1- (2-cyanoethyl) -ε-caprola
Synthesis of cuta 250 g of ε-caprolactam was added to isopropanol 125
0.5 g of potassium hydroxide was added, and 152 g of acrylonitrile was added dropwise at 70 to 80 ° C. over 2 hours while stirring. After the dropping yield, the reaction was further continued at 80 to 90 ° C. for 2 hours to give 1- (2-cyanoethyl) -ε-
527 g of caprolactam reaction liquid was obtained. This reaction was repeated and the resulting reaction solution was used as it is for the synthesis of 1- (3-aminopropyl) -ε-caprolactam shown in Example 1 and Example 2. In addition, some reaction liquid
Neutralize with 0% sulfuric acid and then distill under reduced pressure to give 156-161.
1- (2-cyanoethyl)-[epsilon] -caprolactam having a purity of 94% was obtained at [deg.] C / 3 mmHg. (Production Example 2) 1- (2-cyanoethyl) -2-pyrrolide
Synthesis of 2-pyrrolidone 250 g of 2-pyrrolidone was dissolved in 125 g of isopropanol, 0.5 g of potassium hydroxide was added, and 203 g of acrylonitrile was added dropwise at 70-75 ° C. over 1 hour while stirring. After the dropping yield, the reaction was further continued at 80 to 85 ° C. for 2 hours to obtain 1- (2-cyanoethyl) -2-pyrrolidone reaction liquid 576 g. This product was used as it was for the synthesis of 1- (3-aminopropyl) -2-pyrrolidone shown in Example 3. (Example 1) 1- (3-aminopropyl) -ε-capro
Synthesis of lactam 1- (2-cyanoethyl) -ε-obtained from Production Example 1 was placed in an autoclave equipped with a stirrer, thermometer, and hydrogen introduction tube.
Caprolactam reaction liquid 462g and Raney cobalt catalyst (JGC Chemical Co., Ltd. N-354D) 12g (pure content) were put, temperature 125-135 degreeC, 35-40 kg / cm < 2 >.
Hydrogenated under hydrogen pressure. After absorbing a calculated amount of hydrogen, the mixture was cooled and allowed to stand, and the catalyst layer and the solvent layer that sank in the lower portion were separated to obtain 456 g of a solvent layer. When this was analyzed by gas chromatography, no unreacted raw material was detected and the purity of the target product was 86% (excluding the solvent). This one
After filtration, the solvent was distilled off and used for the synthesis of 1,8-diazabicyclo [5.4.0] -7-undecene shown in Reference Example 3. Separately, the same reaction was performed, and the obtained reaction solution was distilled under reduced pressure to obtain 1- (3-aminopropyl) -ε-caprolactam having a purity of 97% at 140-141 ° C./3 mmHg. Infrared absorption spectrum νcm -1 (neat): 292
8.2, 2858.7, 1633.4, 1486.0,
1444.9, 1425.1, 1352.5, 119
8.5, 1082.5, 975.8. Nuclear magnetic resonance spectrum (400 MHz, CDCl 3 ) δ
ppm: 1.57 to 1.76 (8H, m), 2.51
2.54 (2H, m), 2.69 (2H, t, J = 6.
6 Hz), 3.32 to 3.34 (2H, m), 3.46
(2H, t, J = 6.9Hz), 7.27 (2H,
s). (Example 2) 1- (3-aminop
Synthesis of ropyl) -ε-caprolactam The catalyst layer deposited in the lower portion obtained in Example 1 and the reaction liquid of 1- (2-cyanoethyl) -ε-caprolactam obtained in Production Example 1 (469 g) were reacted in the same manner as in Example 1. , And the solvent layer 469g was obtained. When this was analyzed by gas chromatography, no unreacted raw material was detected and the purity of the target product was 89%.
(Excluding the solvent). Table 1 shows the results such as yield and purity when this reaction was repeated 5 times in total. Table 1 1 cycle 2 cycles 3 cycles 4 cycles 5 cycles Solvent layer yield 99% 100% 99% 100% 100% GC purity 86% 89% 88% 89% 85% Unreacted raw material Not detected Not detected Not detected Not detected Not detected (Example 3) 1- (3-aminopropyl) -2-pyrroli
Synthesis of Don 1- (2-cyanoethyl) -2-obtained from Production Example 2 in an autoclave equipped with a stirrer, a thermometer, and a hydrogen introduction tube.
Pyrrolidone reaction liquid 500 g and Raney cobalt catalyst (JGC Chemical Co., Ltd. N-354D) 10.9 g (purity)
, Temperature 125-135 ℃, 35-40kg / cm
2 Hydrogenated under hydrogen pressure. After absorbing a calculated amount of hydrogen, the mixture was cooled and allowed to stand, and the catalyst layer and the solvent layer that sank in the lower portion were separated to obtain 500 g of a solvent layer. When this was analyzed by gas chromatography, no unreacted raw material was detected and the purity of the target product was 98% (excluding the solvent). In addition, the solvent layer was filtered, the solvent was distilled off, and the solvent layer was distilled under reduced pressure.
1- (3-aminopropyl) -2-pyrrolidone having a purity of 98% was obtained at -123 ° C / 4 mmHg. Reference Example 1 1,8-diazabicyclo [5.4.0]-
Synthesis of 7-undecene After filtering 456 g of the solvent layer of the 1- (3-aminopropyl) -ε-caprolactam reaction solution obtained from Example 1, the solvent was distilled off, and 169 g of xylene and p-toluenesulfonic acid mono- 4.5 g of a water salt was added, and the mixture was refluxed and dehydrated at 145-165 ° C. for 13 hours. The resulting reaction mixture was neutralized with 1.5 g of 50% sodium hydroxide and then distilled under reduced pressure to give 133-
233 g of 1,8-diazabicyclo [5.4.0] -7-undecene having a purity of 99% was obtained at 137 ° C./20 mmHg. Obtained 1,8-diazabicyclo [5.4.0]-
7-Undecene had the same infrared absorption spectrum and gas chromatograph retention time as those of the product manufactured by Tokyo Chemical Industry Co., Ltd.
【００２８】[0028]
【発明の効果】本発明は、脱ハロゲン化剤又はウレタン
硬化触媒として有用である、ビシクロ誘導体を製造する
ための重要中間体である３−アミノプロピル誘導体の製
造法であり、ラネーコバルト触媒を用いているため、ラ
ネーニッケル触媒を用いる従来法に比べ、触媒の発火性
が弱く、また液体アンモニアを用いないため、操作性、
作業環境の面で著しく改善され、且つ触媒を繰り返し使
用できるため経済性に優れている。INDUSTRIAL APPLICABILITY The present invention is a method for producing a 3-aminopropyl derivative which is an important intermediate for producing a bicyclo derivative, which is useful as a dehalogenating agent or a urethane curing catalyst, and which uses a Raney cobalt catalyst. Therefore, compared to the conventional method using a Raney nickel catalyst, the ignitability of the catalyst is weak, and since liquid ammonia is not used, operability,
The work environment is remarkably improved, and the catalyst can be used repeatedly, so that it is economical.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4C069 AB12 BB02 BB33 BC12 CC19 4G069 AA02 AA08 BB03A BB03B BC67A BC67B CB06 CB77 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4C069 AB12 BB02 BB33 BC12 CC19 4G069 AA02 AA08 BB03A BB03B BC67A BC67B CB06 CB77
Claims (5)
示す。）を有する２−シアノエチル誘導体を、ラネーコ
バルトの存在下、水素添加することを特徴とする、下記
一般式（II）を有する３−アミノプロピル誘導体（II）
（式中、ｎは１乃至４を示す。）の製造法。 【化１】 1. A 2-cyanoethyl derivative having the following general formula (I) (wherein n represents 1 to 4) is hydrogenated in the presence of Raney cobalt. 3-Aminopropyl derivative having (II) (II)
(In the formula, n represents 1 to 4). [Chemical 1]
用することを特徴とする、請求項１に記載の製造法。2. Process according to claim 1, characterized in that 0.05 to 10% of Raney cobalt is used.
を特徴とする、請求項１又は２に記載の製造法。3. The manufacturing method according to claim 1, wherein Raney cobalt is repeatedly used.
ずれか一項に記載の製造法。4. The method according to any one of claims 1 to 3, wherein n is 1 or 3.
一項に記載の製造法。5. The production method according to claim 1, wherein n is 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003015496A JP2003286257A (en) | 2002-01-24 | 2003-01-24 | Method for producing 3-aminopropyl derivative |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-15848 | 2002-01-24 | ||
| JP2002015848 | 2002-01-24 | ||
| JP2003015496A JP2003286257A (en) | 2002-01-24 | 2003-01-24 | Method for producing 3-aminopropyl derivative |
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| Publication Number | Publication Date |
|---|---|
| JP2003286257A true JP2003286257A (en) | 2003-10-10 |
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ID=29253163
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|---|---|---|---|
| JP2003015496A Pending JP2003286257A (en) | 2002-01-24 | 2003-01-24 | Method for producing 3-aminopropyl derivative |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100005336A1 (en) | 2021-03-08 | 2022-09-08 | Versalis Spa | METHOD FOR THE PREPARATION OF AMIDINE. |
| WO2022189911A1 (en) | 2021-03-08 | 2022-09-15 | Versalis S.P.A. | Method for preparation of amidines |
| IT202200018231A1 (en) | 2022-09-07 | 2024-03-07 | Versalis Spa | METHOD FOR PREPARATION OF AMIDINES FROM N-(ALKYL LACTAMS) |
-
2003
- 2003-01-24 JP JP2003015496A patent/JP2003286257A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100005336A1 (en) | 2021-03-08 | 2022-09-08 | Versalis Spa | METHOD FOR THE PREPARATION OF AMIDINE. |
| WO2022189910A1 (en) | 2021-03-08 | 2022-09-15 | Versalis S.P.A. | Method for preparing amidines |
| WO2022189911A1 (en) | 2021-03-08 | 2022-09-15 | Versalis S.P.A. | Method for preparation of amidines |
| IT202200018231A1 (en) | 2022-09-07 | 2024-03-07 | Versalis Spa | METHOD FOR PREPARATION OF AMIDINES FROM N-(ALKYL LACTAMS) |
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