JPH11180900A - Production of homoallylamines - Google Patents
Production of homoallylaminesInfo
- Publication number
- JPH11180900A JPH11180900A JP9353909A JP35390997A JPH11180900A JP H11180900 A JPH11180900 A JP H11180900A JP 9353909 A JP9353909 A JP 9353909A JP 35390997 A JP35390997 A JP 35390997A JP H11180900 A JPH11180900 A JP H11180900A
- Authority
- JP
- Japan
- Prior art keywords
- homoallylamines
- group
- formula
- producing
- surfactant
- 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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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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、ホモアリ
ルアミン類の製造方法に関するものである。さらに詳し
くは、この出願の発明は、各種の医薬、農薬、香料、潤
滑剤、染料、合成樹脂等の合成中間体等として有用な、
ホモアリルアミン類の製造方法に関するものである。TECHNICAL FIELD The invention of this application relates to a method for producing homoallylamines. More specifically, the invention of this application is useful as various pharmaceuticals, agricultural chemicals, fragrances, lubricants, dyes, synthetic intermediates such as synthetic resins, etc.
The present invention relates to a method for producing homoallylamines.
【０００２】[0002]
【従来の技術とその課題】各種化学品の合成中間体とし
て反応性の高いアリル基を持つホモアリルアミン類の製
造法としては、有機イミン化合物をアリル化試薬として
の有機アリル化錫化合物と、有機溶媒中においてルイス
酸の存在下に反応させて合成する方法が知られている。2. Description of the Related Art As a method for producing a homoallylamine having a highly reactive allyl group as an intermediate for synthesizing various chemicals, an organic allylated tin compound as an allylating reagent and an organic allylated tin compound as an allylating reagent are used. There is known a method of performing synthesis by reacting in the presence of a Lewis acid in a solvent.
【０００３】しかしながら、この従来の方法において
は、水への感応性の高いイミン類、ルイス酸そして有機
錫化合物を用いることから、微量の水分が存在する場合
でもホモアリルアミン類の合成反応は進行しないという
問題があった。 (P.A.Griecoand A.Bahsas, J.Org.Che
m., 1987, 52, 1378；H.Nakamura, H.Iwama andY.Yamam
oto, J.Am.Chem.Soc., 1996, 118, 6641) 近年、一部の希土類金属化合物が水溶液中でもルイス酸
として作用することが見い出されて以来、アルドール反
応などが含水有機溶媒中でも進行することが明らかとな
ったが、これらの場合でも溶媒の主成分としての有機溶
媒が必要であった。さらにこれら含水有機溶媒中での合
成反応の中にもイミンのアリル化の例は無い。However, in this conventional method, since imines, Lewis acids and organotin compounds having high sensitivity to water are used, the synthesis reaction of homoallylamine does not proceed even in the presence of a trace amount of water. There was a problem. (PAGriecoand A. Bahsas, J. Org. Che
m., 1987, 52 , 1378; H. Nakamura, H. Iwama and Y. Yamam
oto, J. Am. Chem. Soc., 1996, 118 , 6641) In recent years, since it was found that some rare earth metal compounds act as Lewis acids in aqueous solutions, aldol reactions etc. proceed in aqueous organic solvents. However, even in these cases, an organic solvent was required as a main component of the solvent. Furthermore, there is no example of imine allylation in the synthesis reaction in these aqueous organic solvents.
【０００４】水溶液反応は、高価な有機溶剤が不要であ
って、引火性や爆発性が無く安全性が高く、人体への悪
影響が無いことや、環境にやさしく、廃棄処理が容易で
あるという優れた利点を持つことから、ホモアリルアミ
ン類の製造においても、有機溶媒を使用することなし
に、水系反応として収率よく合成する方法を実現するこ
とが求められていた。The aqueous solution reaction does not require an expensive organic solvent, has no flammability or explosive property, has high safety, has no adverse effect on human bodies, is environmentally friendly, and is easy to dispose of. Therefore, in the production of homoallylamines, it has been required to realize a method of synthesizing with good yield as an aqueous reaction without using an organic solvent.
【０００５】[0005]
【課題を解決するための手段】この出願は、以上のとお
りの課題を解決するものとして、まず第１の発明とし
て、次式（１）The present invention solves the above-mentioned problems, and firstly, as a first invention, the following formula (1)
【０００６】[0006]
【化５】 Embedded image
【０００７】（式中のＲ1 およびＲ2 は、各々、官能基
を有してもよい炭化水素基もしくは複素環基を示す）で
表わされるホモアリルアミン類の製造方法であって、次
式（II）(Wherein R 1 and R 2 each represent a hydrocarbon group or a heterocyclic group which may have a functional group). II)
【０００８】[0008]
【化６】 Embedded image
【０００９】（Ｒ1 は前記と同一のものを示す）で表わ
されるアルデヒド化合物と、次式（III)[0009] and an aldehyde compound (R 1 is the shows the same thing as) represented by the following formula (III)
【００１０】[0010]
【化７】 Embedded image
【００１１】（Ｒ2 は前記と同一のものを示す）で表わ
されるアミン化合物並びにアリル化試薬とを、希土類ル
イス酸触媒と界面活性剤の存在下に水媒体中において反
応させることを特徴とするホモアリルアミン類の製造方
法を提供する。また、この出願は、上記第１の発明に関
連して、第２の発明として、アリル化試薬が、次式（I
V）The amine compound represented by the formula (R 2 is the same as described above) and an allylating reagent are reacted in an aqueous medium in the presence of a rare earth Lewis acid catalyst and a surfactant. Provided is a method for producing homoallylamines. In addition, this application relates to the above-mentioned first invention, as a second invention, wherein the allylating reagent has the following formula (I)
V)
【００１２】[0012]
【化８】 Embedded image
【００１３】（Ｍは、ＳｎまたはＧｅを示し、Ｒは、ハ
ロゲン原子または炭化水素基を示し、１≦ｎ≦４である
ことを示す）で表わされる有機金属化合物であるホモア
リルアミン類の製造方法を、第３の発明として、希土類
ルイス酸触媒は、Ｓｃ、Ｙ、およびランタノイド金属の
群に属する元素の化合物であるホモアリルアミン類の製
造方法を、第４の発明として、界面活性剤はアニオン性
界面活性剤であるホモアリルアミン類の製造方法をも提
供する。(M represents Sn or Ge, R represents a halogen atom or a hydrocarbon group and represents 1 ≦ n ≦ 4), and a method for producing homoallylamines which are organometallic compounds represented by the formula: As a third invention, a rare earth Lewis acid catalyst is a method for producing homoallylamines, which are compounds of elements belonging to the group of Sc, Y, and lanthanoid metals. As a fourth invention, a surfactant is anionic. There is also provided a method for producing a homoallylamine which is a surfactant.
【００１４】[0014]
【発明の実施の形態】この出願の発明は以上のとおりの
特徴を持つものであるが、以下にその実施の形態につい
て詳細に説明する。まず、発明の目的化合物としてのホ
モアリルアミン類と、合成原料としてのアルデヒド化合
物並びにアミン化合物であるが、このものは前記のとお
りの式（Ｉ）（II）（III)で表わされるが、式中のＲ1
およびＲ2 としての炭化水素基としては、脂肪族炭化水
素基、脂環族炭化水素基、芳香族炭化水素基、芳脂肪族
炭化水素基のうちの各種のものであってよく、炭化水素
環を有する場合には、単環もしくは多環のいずれでもよ
い。複素環基の場合も同様に各種のものでよく、ヘテロ
原子として酸素、窒素、硫黄等の各種のものを持つ３員
環以上の単環または多環のものの各種のものでよい。官
能基についても、ホモアリルアミン類の合成反応を阻害
することのない任意のものを有していてもよく、炭化水
素基、ハロゲン原子、アルコキシ基、エステル基、アシ
ルオキシ基、ニトロ基、シアノ基、チオエステル基、チ
オエーテル基、その他各種のものであってよい。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the features as described above, and the embodiments will be described in detail below. First, a homoallylamine as an object compound of the present invention, an aldehyde compound and an amine compound as raw materials for synthesis, which are represented by the formulas (I), (II) and (III) as described above, R 1
And the hydrocarbon group as R 2 may be any one of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic hydrocarbon group. When it has, it may be either monocyclic or polycyclic. In the case of the heterocyclic group, various types may be similarly used, and various types of monocyclic or polycyclic three or more membered rings having various types of hetero atoms such as oxygen, nitrogen, sulfur and the like may be used. The functional group may have any one that does not inhibit the synthesis reaction of homoallylamines, and may have a hydrocarbon group, a halogen atom, an alkoxy group, an ester group, an acyloxy group, a nitro group, a cyano group, It may be a thioester group, a thioether group or other various groups.
【００１５】前記の式（II）で表わされるアルデヒド化
合物としては、たとえばその具体例では、ベンズアルデ
ヒド、ｐ−クロルベンズアルデヒド、ｍ−クロルベンズ
アルデヒド、ｐ−メトキシベンズアルデヒド、ｏ，ｐ−
ジメチルベンズアルデヒド、フェニルエチルアルデヒ
ド、ｎ−ヘキシルアルデヒド、ｎ−ブチルアルデヒド、
ナフチルアルデヒド、桂皮アルデヒド、シクロヘキシル
メチルアルデヒド、２−チオフェニルアルデヒド、フル
フリルアルデヒド等が挙げられる。また、式（III)で表
わされるアミン化合物としては、アニリン、ｐ−クロル
アニリン、ｐ−メトキシアニリン、ナフチルアミン、ｐ
−エチルアニリン、ｎ−ブチルアミン、ｉｓｏ−ブチル
アミン、シクロヘキシルアミン、４−メトキシシクロヘ
キシルアミン等が挙げられる。Examples of the aldehyde compound represented by formula (II) include, for example, benzaldehyde, p-chlorobenzaldehyde, m-chlorobenzaldehyde, p-methoxybenzaldehyde, o, p-
Dimethylbenzaldehyde, phenylethylaldehyde, n-hexylaldehyde, n-butyraldehyde,
Naphthyl aldehyde, cinnamaldehyde, cyclohexyl methyl aldehyde, 2-thiophenyl aldehyde, furfuryl aldehyde and the like can be mentioned. Examples of the amine compound represented by the formula (III) include aniline, p-chloroaniline, p-methoxyaniline, naphthylamine, and p-chloroaniline.
-Ethylaniline, n-butylamine, iso-butylamine, cyclohexylamine, 4-methoxycyclohexylamine and the like.
【００１６】ホモアリルアミン類の製造のために反応さ
せるアリル化試薬については、アリル基の導入のための
反応活性を持つ化合物であれば任意のものでよいが、な
かでも、この発明においては、前記の式（IV）で表わさ
れるＳｎまたはＧｅの有機金属化合物を使用することが
考慮される。たとえばこれらの具体例としては、テトラ
アリルスズ、アリルトリメチルスズ、アリルトリクロロ
スズ、テトラアリルゲルマニウム、アリルトリエチルゲ
ルマニウム等が挙げられる。The allylating reagent to be reacted for the production of homoallylamines is not particularly limited as long as it has a reaction activity for introducing an allyl group. The use of an organometallic compound of Sn or Ge represented by the formula (IV) is considered. For example, specific examples thereof include tetraallyl tin, allyl trimethyl tin, allyl trichlorotin, tetraallyl germanium, allyl triethyl germanium, and the like.
【００１７】この発明のホモアリルアミン類の製造にお
ける前記のアルデヒド化合物、アミン化合物並びにアリ
ル化試薬の使用割合については、一般的には、モル比と
して、アルデヒド化合物：アミン化合物：アリル化試薬
＝１：０．５〜２：０．２〜２とすることが考慮され
る。また、この発明の製造方法では、希土類ルイス酸触
媒と界面活性剤とを反応系に存在させる。この際の希土
類ルイス酸触媒としては、Ｓｃ、Ｙ、ランタノイドに属
する金属元素の化合物が好適に使用される。たとえばこ
れら金属元素と炭素原子とが結合している金属化合物、
金属アルコラート、金属フェノレート、金属カルボキシ
レート、金属錯体等々の各種のものであってよく、より
好ましいものとしては、Ｓｃ（ＯＴｆ）3 として表わさ
れるスカンジウムトリフレート等が例として挙げられ
る。In the production of the homoallylamines of the present invention, the use ratio of the aldehyde compound, the amine compound and the allylating reagent is generally represented by a molar ratio of aldehyde compound: amine compound: allylating reagent = 1: 1. 0.5 to 2: 0.2 to 2 is considered. In the production method of the present invention, a rare earth Lewis acid catalyst and a surfactant are present in a reaction system. As the rare earth Lewis acid catalyst at this time, a compound of a metal element belonging to Sc, Y, or a lanthanoid is preferably used. For example, metal compounds in which these metal elements and carbon atoms are bonded,
Various types such as a metal alcoholate, a metal phenolate, a metal carboxylate, and a metal complex may be used, and a more preferable example is scandium triflate represented by Sc (OTf) 3 .
【００１８】一方、界面活性剤については、アニオン
性、カチオン性、ノニオン性、あるいは両性の界面活性
剤のいずれかのものが考慮されるが、好ましくはアニオ
ン性界面活性剤が、さらには、有機硫酸塩化合物がこの
界面活性剤として用いられる。硫酸塩化合物としては、
たとえば、アルキル硫酸アルカリ金属塩等が例示され
る。On the other hand, as the surfactant, any one of anionic, cationic, nonionic and amphoteric surfactants is considered, and preferably, anionic surfactants are used, A sulfate compound is used as this surfactant. As sulfate compounds,
For example, an alkali metal salt of alkyl sulfate is exemplified.
【００１９】希土類ルイス酸触媒、そして界面活性剤に
ついては、その種類によっても相違するが、一般的には
その使用量は、原料としての前記アルデヒド化合物に対
し、モル比として、希土類ルイス酸触媒１／１００〜１
／４、界面活性剤１／１００〜１／５程度を目安とする
ことができる。反応は、水媒体中で行うが、反応温度に
ついては常温でよく、その範囲としては一般的には０〜
３０℃程度で反応は充分に進行する。反応時間も適宜で
よく、たとえば０．５〜３０時間程度が考慮される。The rare-earth Lewis acid catalyst and the surfactant are different depending on the kind thereof, but generally, the amount of the rare-earth Lewis acid catalyst used is 1 mole as the molar ratio with respect to the aldehyde compound as a raw material. / 100-1
/ 4, about 1/100 to 1/5 surfactant can be used as a guide. The reaction is carried out in an aqueous medium, and the reaction temperature may be room temperature, and the range is generally from 0 to 0.
The reaction proceeds sufficiently at about 30 ° C. The reaction time may be appropriately set, for example, about 0.5 to 30 hours is considered.
【００２０】以下、実施例を示し、さらに詳しく説明す
る。Hereinafter, the present invention will be described in more detail with reference to examples.
【００２１】[0021]
【実施例】実施例１ ナトリウムドデシル硫酸塩（ＳＤＳ）の３５ｍＭ水溶液
（３ｍｌ）とスカンジウムトリフレート（Ｓｃ（ＯＴ
ｆ）3 ）（０．１ｍｍｏｌ）とを、表１に示した各種の
アルデヒド化合物（０．６５ｍｍｏｌ）、アミン化合物
（０．５ｍｍｏｌ）並びにアリルトリブチルスズ（０．
７５ｍｍｏｌ）と混合し、室温において、２０時間攪拌
した。 EXAMPLE 1 A 35 mM aqueous solution (3 ml) of sodium dodecyl sulfate (SDS) and scandium triflate (Sc (OT)
f) 3 ) (0.1 mmol) with various aldehyde compounds (0.65 mmol), amine compounds (0.5 mmol) and allyltributyltin (0.
75 mmol) and stirred at room temperature for 20 hours.
【００２２】その後、水および酢酸エチルで希釈し、イ
オン交換樹脂アンバーライトＩＲＨ９６ＳＢを加え、１
０分間攪拌した後に濾過した。濾液を酢酸エチルで抽出
処理し、有機相を乾燥、濾過し、濃縮した。得られた粗
生成物をシリカゲル・カラムクロマトグラフィーにより
精製し、表１に示したホモアリルアミン類を得た。Thereafter, the mixture was diluted with water and ethyl acetate, and ion-exchange resin Amberlite IRH96SB was added.
After stirring for 0 minutes, the mixture was filtered. The filtrate was extracted with ethyl acetate and the organic phase was dried, filtered and concentrated. The obtained crude product was purified by silica gel column chromatography to obtain homoallylamines shown in Table 1.
【００２３】表１からは、目的とするアリルアミン類が
高収率で得られることがわかる。Table 1 shows that the desired allylamines can be obtained in high yield.
【００２４】[0024]
【表１】 [Table 1]
【００２５】実施例２ 前記実施例１において、ベンズアルデヒドとアニリンと
を用い、ＳＤＳの使用量を変化させて同様に室温におい
て反応を行った。その結果を表２に示した。Ｓｃ（ＯＴ
ｆ）3 とＳＤＳの両者を使用しない場合、ホモアリルア
ミン類は得られないことがわかる。 Example 2 A reaction was carried out at room temperature in the same manner as in Example 1 except that benzaldehyde and aniline were used and the amount of SDS used was changed. The results are shown in Table 2. Sc (OT
f) It can be seen that when both 3 and SDS are not used, homoallylamines cannot be obtained.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【発明の効果】以上詳しく説明したとおり、この出願の
発明によって、有機溶媒を使用しない水媒体中でのアル
デヒド、アミン、アリル化剤の３成分反応によって高い
収率でホモアリルアミンを得ることが可能となる。そし
て、水媒体中での反応であることから、高価な有機溶媒
が不要で、引火性や爆発性が無く安全性が高く、人体へ
の悪影響もない。そして廃棄処理も容易である。As described in detail above, according to the invention of this application, it is possible to obtain a homoallylamine in a high yield by a three-component reaction of an aldehyde, an amine and an allylating agent in an aqueous medium without using an organic solvent. Becomes Since the reaction is performed in an aqueous medium, an expensive organic solvent is not required, there is no flammability or explosive property, the safety is high, and there is no adverse effect on the human body. And disposal processing is also easy.
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Claims (4)
い炭化水素基もしくは複素環基を示す）で表わされるホ
モアリルアミン類の製造方法であって、次式（II） 【化２】 （Ｒ1 は前記と同一のものを示す）で表わされるアルデ
ヒド化合物と、次式（III) 【化３】 （Ｒ2 は前記と同一のものを示す）で表わされるアミン
化合物並びにアリル化試薬とを、希土類ルイス酸触媒と
界面活性剤の存在下に水媒体中において反応させること
を特徴とするホモアリルアミン類の製造方法。1. The following formula (1) (Wherein R 1 and R 2 each represent a hydrocarbon group or a heterocyclic group which may have a functional group), which is a method for producing homoallylamines represented by the following formula (II): Formula 2 (Wherein R 1 is the same as described above) and an aldehyde compound represented by the following formula (III): (R 2 is the same as above) and an allylating reagent, wherein a homoallylamine is reacted with a rare earth Lewis acid catalyst in the presence of a surfactant in an aqueous medium. Manufacturing method.
たは炭化水素基を示し、１≦ｎ≦４であることを示す）
で表わされる有機金属化合物である請求項１のホモアリ
ルアミン類の製造方法。2. The allylating reagent has the following formula (IV): (M represents Sn or Ge, R represents a halogen atom or a hydrocarbon group, and represents that 1 ≦ n ≦ 4)
The method for producing homoallylamines according to claim 1, which is an organometallic compound represented by the formula:
びランタノイド金属の群に属する元素の化合物である請
求項１または２のホモアリルアミン類の製造方法。3. The method for producing homoallylamines according to claim 1, wherein the rare earth Lewis acid catalyst is a compound of an element belonging to the group of Sc, Y, and a lanthanoid metal.
る請求項１ないし３のいずれかのホモアリルアミン類の
製造方法。4. The method for producing homoallylamines according to claim 1, wherein the surfactant is an anionic surfactant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35390997A JP3569428B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing homoallylamines |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35390997A JP3569428B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing homoallylamines |
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| Publication Number | Publication Date |
|---|---|
| JPH11180900A true JPH11180900A (en) | 1999-07-06 |
| JP3569428B2 JP3569428B2 (en) | 2004-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP35390997A Expired - Fee Related JP3569428B2 (en) | 1997-12-22 | 1997-12-22 | Method for producing homoallylamines |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007719A1 (en) * | 1998-08-04 | 2000-02-17 | Japan Science And Technology Corporation | Method of reaction in water catalyzed by lewis acid |
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1997
- 1997-12-22 JP JP35390997A patent/JP3569428B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007719A1 (en) * | 1998-08-04 | 2000-02-17 | Japan Science And Technology Corporation | Method of reaction in water catalyzed by lewis acid |
| US6525227B1 (en) | 1998-08-04 | 2003-02-25 | Japan Science And Technology Corporation | Method of reaction in water catalyzed by Lewis acid |
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| Publication number | Publication date |
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| JP3569428B2 (en) | 2004-09-22 |
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