KR20090122819A - Novel catalyst for intermolecular hydroamination, and process for preparing cyclic imine compounds using them - Google Patents

Novel catalyst for intermolecular hydroamination, and process for preparing cyclic imine compounds using them Download PDF

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KR20090122819A
KR20090122819A KR1020080048813A KR20080048813A KR20090122819A KR 20090122819 A KR20090122819 A KR 20090122819A KR 1020080048813 A KR1020080048813 A KR 1020080048813A KR 20080048813 A KR20080048813 A KR 20080048813A KR 20090122819 A KR20090122819 A KR 20090122819A
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이필호
김현석
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강원대학교산학협력단
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract

PURPOSE: A novel catalyst for intermolecular hydroamination and a method for manufacturing cyclic imine compounds using the catalyst are provided to produce the novel catalyst by using an amino Alkynes derivative. CONSTITUTION: A novel catalyst for intermolecular hydroamination uses a catalyst composition including a titanium-amino metal compound, a 4B family metal complex, a 4B family metal compound and specified ligand. The catalyst for intermolecular hydroamination is a titanium - amino compound indicated as a chemical formula 2. The chemical formula 2 is TiClp(NR2)q. R is a straight-chain or a branched-chain alkyl group of C1~C6. P is 0 or 1 and p+q=4. The catalyst is the 4B family metal complex indicated by a chemical formula 3a, 3b or 3c. X and Q is one of the straight-chain or a branched-chain alkyl group of C1~C6, a phenyl radical or a benzyl radical. M is 4B family metal atoms.

Description

분자내 하이드로아미네이션 반응용 신규 촉매와, 이 촉매를 이용한 고리형 이민 화합물의 제조방법{Novel catalyst for intermolecular hydroamination, and process for preparing cyclic imine compounds using them}Novel catalyst for intermolecular hydroamination, and process for preparing cyclic imine compounds using them

본 발명은 분자내 하이드로아미네이션 반응용 신규 촉매와, 이 촉매를 이용한 고리형 이민 화합물의 제조방법에 관한 것이다.The present invention relates to a novel catalyst for intramolecular hydroamination reaction and a method for producing a cyclic imine compound using the catalyst.

보다 상세하게는, 본 발명은 삼중결합을 가지는 아미노알킨 유도체를 분자내 하이드로아미네이션(intermolecular hydroamination)시켜 고리형 이민 화합물을 제조하는 반응에서 우수한 활성을 보이는 타이타늄-아미노 금속화합물과, 4B족 금속 양이온과 특정의 음이온 리간드가 화학결합을 이루고 있는 4B족 금속착물과, 4B족 금속화합물과 특정의 리간드를 포함하는 촉매 조성물을 촉매로 사용하는 용도에 관한 발명과, 상기한 촉매를 사용하여 삼중결합을 가지는 아미노알킨 유도체를 분자내 하이드로아미네이션(intermolecular hydroamination)시켜 하기 화학식 1로 표시되는 고리형 이민 화합물을 제조하는 방법에 관한 발명이다.More specifically, the present invention provides a titanium-amino metal compound and a Group 4B metal cation which exhibit excellent activity in the reaction of preparing an cyclic imine compound by intramolecular hydroamination of an aminoalkyne derivative having a triple bond. The invention relates to the use of a catalyst composition comprising a Group 4B metal complex having a chemical bond with a specific anionic ligand, a Group 4B metal compound and a specific ligand as a catalyst, and a triple bond using the catalyst described above. The present invention relates to a method for preparing a cyclic imine compound represented by the following Chemical Formula 1 by intramolecular hydroamination of an aminoalkyne derivative.

Figure 112008037459202-PAT00001
Figure 112008037459202-PAT00001

상기 화학식 1에서, R1, R2, 및 R3은 서로 같거나 다른 것으로서 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 벤질기, 또는 벤질옥시기를 나타내고; R4는 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 또는 페닐기를 나타내고; n은 1 내지 3의 정수이다. In Formula 1, R 1 , R 2 , and R 3 are the same as or different from each other, and represent a hydrogen atom, a C 1 to C 6 straight or crushed alkyl group, benzyl group, or benzyloxy group; R 4 represents a hydrogen atom, a C 1 to C 6 straight or branched alkyl group, or a phenyl group; n is an integer of 1-3.

아미노알킨(aminoalkyne)의 분자내 하이드로아미네이션(intermolecular hydroamination)을 수행하여 질소를 포함한 고리 화합물을 합성하는 반응에서, 전이금속(transition metal)이 촉매활성을 나타냄에 대해서는 이미 잘 알려져 있다. [Chem. Rev. 1998, 98, 675; Organometallics 2000, 19, 87; Organometallics 2000, 19, 170; Organometallics 2000, 19, 539; J. Am. Chem. Soc. 2000, 122, 9546; Org. Lett. 2000, 2, 1935; J. Am. Chem. Soc. 2001, 123, 2923; Chem. Soc. Rev. 2003, 32, 104; Eur. J. Org. Chem. 2003, 935; Chem. Rev. 2004, 104, 3079] 또한, 전이금속 촉매로서 메탈로센 (metallocene) 촉매들은 대부분이 공기 중이나 수분에 노출되었을 때, 촉매의 활성이 매우 저해된다는 것과 촉매의 다양성 측 면에서 한계점을 지니고 있음에 대해서도 잘 알려져 있다. [Angew. Chem. Int. Ed. 2004, 43, 5542] 그리고, 4B족 전이금속 중에서도 지르코늄만이 분자내 하이드로아미네이션 반응에서 촉매활성이 극대화되므로 4B족 금속은 지르코늄 금속촉매로 제한되며, 그 촉매의 활성은 2차 아미노알켄(aminoalkene) 기질에만 적용되는 단점이 있음에 대해서도 잘 알려져 있다. 따라서 분자내 하이드로아미네이션 반응에 의하여 알칼로이드와 같은 질소를 포함한 고리 화합물을 합성하는 분야에서는, 활성을 극대화할 수 있는 촉매의 개발이 절실히 요구되고 있다.It is well known that transition metals exhibit catalytic activity in the reaction of synthesizing nitrogen-containing ring compounds by performing intramolecular hydroamination of aminoalkyne. Chem. Rev. 1998 , 98 , 675; Organometallics 2000 , 19 , 87; Organometallics 2000 , 19 , 170; Organometallics 2000 , 19 , 539; J. Am. Chem. Soc . 2000 , 122 , 9546; Org. Lett . 2000 , 2 , 1935; J. Am. Chem. Soc . 2001 , 123 , 2923; Chem . Soc . Rev. 2003 , 32 , 104; Eur . J. Org . Chem . 2003 , 935; Chem . Rev. 2004 , 104 , 3079] In addition, most of metallocene catalysts as transition metal catalysts have limitations in that the activity of the catalyst is very impaired when exposed to air or moisture and the diversity of the catalyst. It is well known. Angew. Chem. Int. Ed . 2004 , 43 , 5542] Among the 4B transition metals, only zirconium maximizes the catalytic activity in the intramolecular hydroamination reaction, and therefore, the 4B metal is limited to the zirconium metal catalyst, and the activity of the catalyst is secondary aminoalkene. It is also well known that there are disadvantages that apply only to substrates. Therefore, in the field of synthesizing ring compounds containing nitrogen such as alkaloids by intramolecular hydroamination reaction, the development of a catalyst that can maximize the activity is urgently required.

이에 본 발명에서는 메탈로센 촉매보다 상대적으로 안정한 넌-메탈로센 (non-metallocene) 계열의 4B족 금속을 사용하고, 복잡한 구조의 리간드 보다는 합성이 용이한 특정 구조의 리간드를 선택하되, 아미노알킨 유도체를 기질로 사용하여 고리형 이민 화합물을 합성하기 위한 분자내 하이드로아미네이션 반응에서 우수한 촉매활성을 나타내는 신규 촉매를 개발하였다.Therefore, in the present invention, a non-metallocene-based group 4B metal, which is relatively more stable than a metallocene catalyst, is used, and a ligand having a specific structure that is easy to synthesize is selected, rather than a complex ligand, and an aminoalkyne. Using a derivative as a substrate, a novel catalyst has been developed that exhibits excellent catalytic activity in the intramolecular hydroamination reaction to synthesize cyclic imine compounds.

본 발명은 분자내 하이드로아미네이션 반응용 신규 촉매를 제공하는데 그 목적이 있다.It is an object of the present invention to provide a novel catalyst for intramolecular hydroamination reactions.

본 발명은 상기한 신규 촉매와 기질로서 아미노알킨 유도체를 사용하여 고리형 이민 화합물을 제조하는 방법을 제공하는데 그 목적이 있다.It is an object of the present invention to provide a method for producing a cyclic imine compound using an aminoalkyne derivative as the novel catalyst and substrate described above.

상기한 본 발명의 목적 달성을 위하여, 본 발명은 하기 화학식 2로 표시되는 타이타늄-아미노 화합물을 분자내 하이드로아미네이션 반응용 촉매로 사용하는 용도를 그 특징으로 한다.In order to achieve the above object of the present invention, the present invention is characterized in that the use of the titanium-amino compound represented by the following formula (2) as a catalyst for intramolecular hydroamination reaction.

TiClp(NR2)q TiCl p (NR 2 ) q

상기 화학식 2에서, R은 C1∼C6의 직쇄 또는 분쇄형 알킬기를 나타내고; p는 0 또는 1이고, p+q=4이다.In Chemical Formula 2, R represents a C 1 to C 6 straight or branched alkyl group; p is 0 or 1 and p + q = 4.

또한, 본 발명은 하기 화학식 3a, 3b 또는 3c로 표시되는 4B족 금속착물을 분자내 하이드로아미네이션 반응용 촉매로 사용하는 용도를 그 특징으로 한다.In addition, the present invention is characterized by the use of the Group 4B metal complex represented by the following formula (3a, 3b or 3c) as a catalyst for intramolecular hydroamination reaction.

Figure 112008037459202-PAT00002
Figure 112008037459202-PAT00002

상기 화학식 3a, 3b 또는 3c에서, X 및 Q는 서로 같거나 다른 것으로서 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, tert-부틸을 포함하는 C1∼C6의 직쇄 또는 분쇄형 알킬기, 페닐기, 또는 벤질기를 나타내고; M은 타이타늄(Ti), 지르코늄(Zr)을 포함하는 4B족 금속원자를 나타내고; R은 C1∼C6의 직쇄 또는 분쇄형 알킬기를 나타낸다.In Chemical Formulas 3a, 3b, or 3c, X and Q are the same as or different from each other, and a C 1 to C 6 straight or crushed alkyl group including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert -butyl, Phenyl group or benzyl group; M represents a Group 4B metal atom including titanium (Ti) and zirconium (Zr); R represents a linear or branched alkyl group of C 1 ~C 6.

또한, 본 발명은 4B족 금속화합물과 하기 화학식 4a, 4b 또는 4c로부터 선택된 리간드가 포함된 촉매 조성물을 분자내 하이드로아미네이션 반응용 촉매로 사용하는 용도를 그 특징으로 한다.In addition, the present invention is characterized by the use of a catalyst composition containing a group 4B metal compound and a ligand selected from the following formula (4a, 4b or 4c) as a catalyst for intramolecular hydroamination reaction.

Figure 112008037459202-PAT00003
Figure 112008037459202-PAT00003

상기 화학식 4a, 4b 또는 4c에서, X 및 Q는 서로 같거나 다른 것으로서 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, tert-부틸을 포함하는 C1∼C6의 직쇄 또는 분쇄형 알킬기, 페닐기, 또는 벤질기를 나타낸다.In Chemical Formulas 4a, 4b or 4c, X and Q are the same as or different from each other, and a C 1 to C 6 straight or pulverized alkyl group including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert -butyl, A phenyl group or a benzyl group is represented.

또한, 본 발명은 상기한 타이타늄-아미노 화합물, 4B족 금속착물, 및 촉매 조성물로 이루어진 군으로부터 선택된 촉매 하에서, 하기 화학식 6으로 표시되는 아미노알킨 유도체를 분자내 하이드로아미네이션 반응시켜 하기 화학식 1로 표시되는 고리형 이민 화합물을 제조하는 방법을 그 특징으로 한다.In addition, the present invention is represented by the following formula (1) by intramolecular hydroamination reaction of the amino alkyne derivative represented by the formula (6) under a catalyst selected from the group consisting of the titanium-amino compound, group 4B metal complex, and the catalyst composition It is characterized by a method for producing a cyclic imine compound.

Figure 112008037459202-PAT00004
Figure 112008037459202-PAT00004

[화학식 1][Formula 1]

Figure 112008037459202-PAT00005
Figure 112008037459202-PAT00005

상기 화학식 1 또는 6에서, R1, R2, 및 R3은 서로 같거나 다른 것으로서 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 벤질기, 또는 벤질옥시기를 나타내고; R4는 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 또는 페닐기를 나타내고; n은 1 내지 3의 정수이다. In Formula 1 or 6, R 1 , R 2 , and R 3 are the same as or different from each other, and represent a hydrogen atom, a C 1 -C 6 straight or crushed alkyl group, benzyl group, or benzyloxy group; R 4 represents a hydrogen atom, a C 1 to C 6 straight or branched alkyl group, or a phenyl group; n is an integer of 1-3.

이상에서 설명한 바와 같은 본 발명을 보다 상세히 설명하면 하기와 같다.Referring to the present invention as described above in more detail as follows.

본 발명에서 제안하는 신규 촉매는 타이타늄-아미노 화합물이거나, 4B족 금속이온과 특정 구조의 리간드가 착결합한 금속착물이거나, 또는 4B족 금속화합물과 특정 리간드가 포함된 촉매 조성물일 수 있다. The novel catalyst proposed in the present invention may be a titanium-amino compound, a metal complex in which a group 4B metal ion is bonded to a ligand of a specific structure, or a catalyst composition including a group 4B metal compound and a specific ligand.

본 발명이 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매로서 상기 화학식 2로 표시되는 타이타늄-아미노 화합물을 보다 구체적으로 예시하면, TiCl[N(CH3)2]3, Ti[N(CH3)2]4, Ti[N(CH2CH3)2]4 일 수 있다. 본 발명이 촉매로서 제안하는 타이타늄-아미노 화합물은 아미노알킨 유도체의 분자내 하이드로아미네이션 반응에 사용되어 우수한 촉매활성을 나타낸다.More specifically exemplified by the titanium-amino compound represented by the formula (2) as a catalyst for intramolecular hydroamination reaction, characterized in that the present invention, TiCl [N (CH 3 ) 2 ] 3 , Ti [N (CH 3 ) 2 ] 4 , Ti [N (CH 2 CH 3 ) 2 ] 4 . The titanium-amino compound proposed by the present invention as a catalyst is used in the intramolecular hydroamination reaction of aminoalkyne derivatives and shows excellent catalytic activity.

상기 배경기술에서 이미 설명한 바와 같이, 4B족 금속화합물로서 지르코늄 화합물만이 제한적으로 분자내 하이드로아미네이션 반응에서 활성을 나타내는 것으로 현재까지 보고되어 있다. 그러나, 본 발명이 제안하는 상기 화학식 2로 표시되는 타이타늄-아미노 화합물은 타이타늄 금속 양이온과 화학결합을 이루는 음이온이 Clp(NR2)q으로 특정됨으로써 분자내 하이드로아미네이션 반응에서 우수한 촉매활성을 나타낸다. 따라서, 본 발명은 분자내 하이드로아미네이션 반응용 촉매로서 사용 가능한 4B족 금속의 선택 범위를 확대시키는 효과가 있다.As already described in the background art, only zirconium compounds as Group 4B metal compounds have been reported to present their activity in the intramolecular hydroamination reaction to a limited extent. However, the titanium-amino compound represented by the formula (2) proposed by the present invention exhibits excellent catalytic activity in the intramolecular hydroamination reaction by specifying Cl p (NR 2 ) q as an anion forming a chemical bond with a titanium metal cation. . Therefore, the present invention has the effect of expanding the selection range of the Group 4B metals that can be used as the catalyst for intramolecular hydroamination reaction.

본 발명이 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매로서 4B족 금속착물 또는 촉매 조성물은, 4B족 금속화합물과 특정 구조의 리간드 사이의 리간드 교환 반응 (ligand exchange reaction)을 유도하여 촉매활성을 증진시키는 효과를 얻을 수 있다. 다시 말하면, 본 발명에서는 분자내 하이드로아미네이션 반응용 촉매로서 4B족 금속화합물과 특정 구조의 리간드가 리간드 교환 반응 (ligand exchange reaction) 반응하여 생성된 상기 화학식 3a, 3b, 또는 3c로 표시되는 금속착물을 사용할 수 있고, 또는 4B족 금속화합물과 특정 리간드 예를 들면 상기 화학식 4a, 4b, 또는 4c로 표시되는 화합물을 포함하여 이루어진 촉매 조성물을 분자내 하이드로아미네이션 반응물에 투입하여 인-시츄 (in-situ)로 제조하여 사용할 수도 있다. 상기한 4B족 금속착물 또는 촉매 조성물은 각각 아미노알킨 유도체의 분자내 하이드로아미네이션 반응에 사용되어 우수한 촉매활성을 나타낸다. 제조공정의 단순화 측면에서 볼 때 4B족 금속착물을 합성 및 정제하여 사용하는 것 보다는, 4B족 금속화합물과 리간드를 포함하는 촉매 조성물을 반응에 투입하여 인-시츄 (in-situ)로 제조하여 사용하는 것이 보다 바람직할 수도 있다. Group 4B metal complexes or catalyst compositions as catalysts for intramolecular hydroamidation reactions characterized by the present invention enhance the catalytic activity by inducing a ligand exchange reaction between a Group 4B metal compound and a ligand of a specific structure. It is possible to obtain an effect. In other words, in the present invention, the metal complex represented by Chemical Formulas 3a, 3b, or 3c produced by a ligand exchange reaction between a Group 4B metal compound and a ligand having a specific structure as a catalyst for intramolecular hydroamidation reaction. Or a catalyst composition comprising a Group 4B metal compound and a specific ligand, for example, a compound represented by Formula 4a, 4b, or 4c, may be added to an intramolecular hydro- amination reaction to in-situ. may be prepared and used. The Group 4B metal complexes or catalyst compositions described above are used in intramolecular hydroamination reactions of aminoalkyne derivatives, respectively, and exhibit excellent catalytic activity. In view of the simplification of the manufacturing process, rather than synthesizing and purifying the Group 4B metal complex, a catalyst composition containing a Group 4B metal compound and a ligand is added to the reaction to be prepared in-situ. It may be more desirable.

본 발명의 촉매 조성물로서 포함되는 4B족 금속화합물은, 주기율표상의 4B족 금속 양이온과 적절한 음이온으로 이루어진 통상의 금속 전구체이다. 이때 음이온은 금속 전구체 제조를 위하여 당 분야에서 일반적으로 적용되고 있는 음이온 그룹으로서, 예를 들면 할로겐, 아세테이트, 설페이트, 나이트레이트, 아미노, C1-C6모노알킬아미노, 및 디(C1-C6알킬)아미노 그룹으로부터 선택될 수 있다. 본 발명에서 사용될 수 있는 바람직한 4B족 금속화합물은 하기 화학식 5로 표시될 수 있다.The Group 4B metal compound included as the catalyst composition of the present invention is a common metal precursor composed of Group 4B metal cations on the periodic table and appropriate anions. The anion is an anion group generally applied in the art for the preparation of metal precursors, for example halogen, acetate, sulfate, nitrate, amino, C 1 -C 6 monoalkylamino, and di (C 1 -C 6 alkyl) amino group. Preferred Group 4B metal compounds that can be used in the present invention may be represented by the following formula (5).

MClm(NR2)n MCl m (NR 2 ) n

상기 화학식 5에서, M은 4B족 금속원자를 나타내고; R은 C1∼C6의 직쇄 또는 분쇄형 알킬기, 또는 를 나태내고; m은 0 또는 1 내지 4의 정수이고, n+m=4이다.In Chemical Formula 5, M represents a Group 4B metal atom; R represents a C 1 to C 6 straight or branched alkyl group, or; m is 0 or an integer of 1 to 4, and n + m = 4.

상기 화학식 5로 표시되는 4B족 금속화합물을 구체적으로 예시하면, TiCl4, Ti[OAc]4, Ti[NO2]4, TiCl[N(CH3)2]3, Ti[N(CH3)2]4, Ti[N(CH2CH3)2]4, ZrCl4, Zr[OAc]4, Zr[NO2]4, ZrCl[N(CH3)2]3, Zr[N(CH3)2]4, Zr[N(CH2CH3)2]4 등이다. Specific examples of the Group 4B metal compound represented by Formula 5 include TiCl 4 , Ti [OAc] 4 , Ti [NO 2 ] 4 , TiCl [N (CH 3 ) 2 ] 3 , Ti [N (CH 3 ) 2 ] 4 , Ti [N (CH 2 CH 3 ) 2 ] 4 , ZrCl 4 , Zr [OAc] 4 , Zr [NO 2 ] 4 , ZrCl [N (CH 3 ) 2 ] 3 , Zr [N (CH 3 2 ] 4 , Zr [N (CH 2 CH 3 ) 2 ] 4 and the like.

본 발명의 촉매 조성물을 구성하는 리간드는 분자내에 질소원자(N), 인원자(P), 황원자(S)을 동시에 포함하는 리간드로서, 본 발명에서는 "NPS-리간드"로 명명한다. 본 발명에서 적용될 수 있는 NPS-리간드를 보다 구체적으로 예시하면 하기 화학식 4a, 4b 또는 4c로 표시될 수 있다. The ligand constituting the catalyst composition of the present invention is a ligand containing both nitrogen atom (N), phosphorus atom (P), and sulfur atom (S) at the same time in the molecule, and is named "NPS-ligand" in the present invention. More specifically illustrating the NPS-ligand that can be applied in the present invention can be represented by the following formula 4a, 4b or 4c.

Figure 112008037459202-PAT00006
Figure 112008037459202-PAT00006

상기 화학식 4a, 4b 또는 4c에서, X 및 Q는 각각 상기에서 정의한 바와 같다.In Formula 4a, 4b or 4c, X and Q are as defined above, respectively.

한편, 본 발명은 상기에서 설명한 촉매 존재 하에서 하기 화학식 6으로 표시되는 아미노알킨 유도체를 분자내 하이드로아미네이션 반응시켜, 하기 화학식 1로 표시되는 고리형 이민 화합물을 제조하는 방법을 권리범위로 포함한다. 본 발명에 따른 고리형 이민 화합물의 제조방법을 보다 구체적으로 설명하면 다음과 같다.On the other hand, the present invention includes a method for preparing the cyclic imine compound represented by the following formula (1) by intramolecular hydroamination reaction of the aminoalkyne derivative represented by the following formula (6) in the presence of the catalyst described above as a scope. Hereinafter, the method for preparing the cyclic imine compound according to the present invention will be described in more detail.

Figure 112008037459202-PAT00007
Figure 112008037459202-PAT00007

상기 반응식 1에서, R1, R2, R3, R4, 및 n은 각각 상기에서 정의한 바와 같다.In Scheme 1, R 1 , R 2 , R 3 , R 4 , and n are each as defined above.

본 발명에 따른 고리형 이민 화합물의 제조방법에서는, 반응용매로서 탄소수 6 내지 10의 방향족 탄화수소를 사용한다. 구체적으로는 벤젠, 톨루엔, o-자일 렌, m-자일렌, p-자일렌 등이 사용될 수 있다. 본 발명의 실시예에서는 NMR을 이용하여 수득률을 계산하기 위해 벤젠-d 6, 톨루엔-d 8, 자일렌-d 6를 반응용매로 사용하였고, 이때 기준 물질(internal standard material)로서 1 당량의 파라-자일렌를 첨가하였다. 본 발명을 상업적인 목적으로 적용하는 경우에는 벤젠, 톨루엔, 자일렌의 방향족 탄화수소를 용매로 사용할 수도 있다. 본 발명에 따른 고리형 이민 화합물의 제조방법에서는, 반응온도 범위가 사용된 촉매 및 기질의 종류에 따라 다소 차이가 있는데 통상적으로 실온(20 ℃) 내지 용매의 환류온도를 유지하게 되면, 분자내 하이드로아미네이션은 원활하게 진행된다. 바람직하기로는 65 ℃ 내지 150 ℃의 가열온도 조건을 유지하는 것이다. In the method for producing a cyclic imine compound according to the present invention, an aromatic hydrocarbon having 6 to 10 carbon atoms is used as the reaction solvent. Specifically, benzene, toluene, o- xylene, m- xylene, p- xylene and the like can be used. In an embodiment of the present invention, benzene- d 6 , toluene- d 8 , xylene- d 6 was used as a reaction solvent to calculate the yield using NMR, wherein 1 equivalent of para as an internal standard material was used. Xylene was added. When the present invention is applied for commercial purposes, aromatic hydrocarbons of benzene, toluene and xylene may be used as a solvent. In the method for preparing a cyclic imine compound according to the present invention, the reaction temperature range is slightly different depending on the type of catalyst and substrate used. Generally, if the reflux temperature of the solvent is maintained at room temperature (20 ° C.) to the solvent, The amination goes smoothly. Preferably, the heating temperature is maintained at 65 ° C to 150 ° C.

이하, 제조예 및 실시예를 통하여 본 발명의 구성을 보다 구체적으로 설명하지만, 하기의 제조예 및 실시예들은 본 발명에 대한 이해를 돕기 위한 것으로서, 본 발명의 범위가 여기에 국한되는 것은 아니다. Hereinafter, the structure of the present invention will be described in more detail with reference to Preparation Examples and Examples, but the following Preparation Examples and Examples are provided to assist in understanding the present invention, but the scope of the present invention is not limited thereto.

[제조예] 리간드 및 촉매로서 4B족 금속착물의 합성Preparation Example Synthesis of Group 4B Metal Complexes as Ligands and Catalysts

하기 제조예 1 내지 3에서는, 촉매 조성물에 포함되는 NPS-리간드를 합성하는 예를 기재하였다.In the following Production Examples 1 to 3, an example of synthesizing the NPS-ligand contained in the catalyst composition was described.

제조예 1. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민의 제조 Preparation Example 1. Preparation of N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine

Figure 112008037459202-PAT00008
Figure 112008037459202-PAT00008

질소분위기 하에서 2,2-다이메틸프로판-1,3-다이아민 (255.0 mg, 2.5 mol)과 4-메틸몰포린 (0.66 mL, 6.0 mmol)을 CH2Cl2 (5 mL)에 녹인 다음, 이 용액에 클로로다이아이소프로필포스핀 (0.8 mL, 5.0 mol)을 CH2Cl2 (3 mL)에 녹인 후에 0 ℃ 에서 천천히 첨가하였다. 실온에서 12시간 교반한 후에 황 (170 mg, 5.3 mol)을 첨가한 후 실온에서 2시간 교반하였다. 감압으로 용매를 제거한 뒤에 실리카겔 크로마토그래피 컬럼(에틸아세테이트/헥산=1/20)으로 분리하고 메틸사이클로헥산에서 재결정하여, 상기 표제화합물을 흰색 고체(670 mg, 68 %)로 얻었다.Dissolve 2,2-dimethylpropane-1,3-diamine (255.0 mg, 2.5 mol) and 4-methylmorpholine (0.66 mL, 6.0 mmol) in CH 2 Cl 2 (5 mL) under a nitrogen atmosphere. Chlorodiisopropylphosphine (0.8 mL, 5.0 mol) was dissolved in CH 2 Cl 2 (3 mL) and slowly added to this solution at 0 ° C. After stirring for 12 hours at room temperature, sulfur (170 mg, 5.3 mol) was added, followed by stirring at room temperature for 2 hours. The solvent was removed under reduced pressure, and then separated by silica gel chromatography column (ethyl acetate / hexane = 1/20) and recrystallized from methylcyclohexane to give the title compound as a white solid (670 mg, 68%).

녹는점 143-144 ℃; 1H NMR (500 MHz, C6D6, 25 ℃) δ 2.95 (t, J = 8.0 Hz, 4H, CH 2), 2.67 (q, J = 8.0 Hz, 2H, NH), 2.10 (septet, J = 7.0 Hz, 4H, CH), 1.11 (d, J = 7.0 Hz, 6H, CHCH 3), 1.07 (t, J = 5.75 Hz, 12H, CHCH 3), 1.03 (d, J = 7.0 Hz, 6H, CHCH 3), 0.82 (s, 6H, C(CH 3)2). Melting point 143-144 ° C .; 1 H NMR (500 MHz, C 6 D 6 , 25 ° C) δ 2.95 (t, J = 8.0 Hz, 4H, C H 2 ), 2.67 (q, J = 8.0 Hz, 2H, N H ), 2.10 (septet , J = 7.0 Hz, 4H, C H ), 1.11 (d, J = 7.0 Hz, 6H, CHC H 3 ), 1.07 (t, J = 5.75 Hz, 12H, CHC H 3 ), 1.03 (d, J = 7.0 Hz, 6H, CHC H 3 ), 0.82 (s, 6H, C (C H 3 ) 2 ).

제조예 2. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-1,2-페닐렌다이아민의 제조 Preparation Example 2 Preparation of N, N' -bis ( P, P'-diisopropylthiophosphinyl) -1,2-phenylenediamine

Figure 112008037459202-PAT00009
Figure 112008037459202-PAT00009

질소분위기 하에서 1,2-페닐렌다이아민 (270 mg, 2.5 mol)과 4-메틸몰포린 (0.66 mL, 6.0 mmol)과 클로로다이아이소프로필포스핀 (0.8 mL, 5.0 mol)을 톨루엔 (16 mL)에 녹인 후에, 70 ℃ 에서 12시간 교반한 후에 황 (170 mg, 5.3 mol)을 첨가한 후 실온에서 2시간 교반하였다. 감압으로 용매를 제거한 뒤에 실리카겔 크로마토그래피 컬럼(에틸아세테이트/헥산=1/20)으로 분리하고 메틸사이클로헥산에서 재결정여, 상기 표제화합물을 흰색 고체(585 mg, 58 %)로 얻었다. 1,2-phenylenediamine (270 mg, 2.5 mol), 4-methylmorpholine (0.66 mL, 6.0 mmol) and chlorodiisopropylphosphine (0.8 mL, 5.0 mol) were added to toluene (16 mL) under a nitrogen atmosphere. ), And stirred at 70 ° C for 12 hours, followed by addition of sulfur (170 mg, 5.3 mol) and then at room temperature for 2 hours. The solvent was removed under reduced pressure, and then separated by silica gel chromatography column (ethyl acetate / hexane = 1/20) and recrystallized from methylcyclohexane to give the title compound as a white solid (585 mg, 58%).

녹는점 114-115 ℃; 1H NMR (300 MHz, CDCl3, 25 ℃) δ 7.34 (dd, J = 6.0, 3.6 Hz, 2H), 6.98 (dd, J = 6.0, 3.6 Hz, 2H), 5.30 (bs, 2H), 2.33 (septet, J = 6.9 Hz, 4H), 1.26 (d, J = 6.9 Hz, 12H), 1.25 (d, J = 6.9 Hz, 12H). Melting point 114-115 ° C .; 1 H NMR (300 MHz, CDCl 3 , 25 ° C) δ 7.34 (dd, J = 6.0, 3.6 Hz, 2H), 6.98 (dd, J = 6.0, 3.6 Hz, 2H), 5.30 (bs, 2H), 2.33 (septet, J = 6.9 Hz, 4H), 1.26 (d , J = 6.9 Hz, 12H), 1.25 (d, J = 6.9 Hz, 12H).

제조예 3. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,3-다이메틸-2,3-부탄다이아민의 제조 Preparation Example 3 Preparation of N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,3-dimethyl-2,3-butanediamine

Figure 112008037459202-PAT00010
Figure 112008037459202-PAT00010

질소분위기 하에서 2,3-다이메틸프로판-2,3-다이아미노부탄 (290 mg, 2.5 mol)과 4-메틸몰포린 (0.66 mL, 6.0 mmol)과 클로로다이아이소프로필포스핀 (0.8 mL, 5.0 mol)을 톨루엔 (16 mL)에 녹인 후에, 70 ℃ 에서 12시간 교반 후에 황 (170 mg, 5.3 mol)을 첨가한 후 실온에서 2시간 교반하였다. 감압으로 용매를 제거한 뒤에 실리카겔 크로마토그래피 컬럼(에틸아세테이트/헥산=1/20)으로 분리하고 메틸사이클로헥산에서 재결정하여, 상기 표제화합물을 희색 고체(440 mg, 43 %)로 얻었다.2,3-dimethylpropane-2,3-diaminobutane (290 mg, 2.5 mol), 4-methylmorpholine (0.66 mL, 6.0 mmol) and chlorodiisopropylphosphine (0.8 mL, 5.0) under nitrogen atmosphere mol) was dissolved in toluene (16 mL), and then stirred at 70 ° C. for 12 hours, followed by addition of sulfur (170 mg, 5.3 mol), followed by stirring at room temperature for 2 hours. The solvent was removed under reduced pressure, separated by silica gel chromatography column (ethyl acetate / hexane = 1/20) and recrystallized from methylcyclohexane to obtain the title compound as a white solid (440 mg, 43%).

녹는점 147-148 ℃; 1H NMR (300 MHz, CDCl3, 25 ℃) δ 2.69 (bs, 2H, NH), 2.19 (septet, J = 6.9 Hz, 4H, CH), 1.44 (s, 12H, CH3), 1.22 (d, J = 6.9 Hz, 12H, CH3), 1.19 (d, J = 6.9 Hz, 12H, CH3).Melting point 147-148 ° C .; 1 H NMR (300 MHz, CDCl 3 , 25 ° C) δ 2.69 (bs, 2H, NH), 2.19 (septet, J = 6.9 Hz, 4H, CH), 1.44 (s, 12H, CH 3 ), 1.22 (d, J = 6.9 Hz, 12H, CH 3 ), 1.19 ( d, J = 6.9 Hz, 12H, CH 3 ).

하기 제조예 4 내지 7에서는, 하이드로아미네이션 반응용 촉매로서 4B족 금속착물을 합성하는 예를 기재하였다.In the following Production Examples 4 to 7, an example of synthesizing a Group 4B metal complex as a catalyst for a hydro amination reaction was described.

제조예 4. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-1,2-페닐렌다이아민일 비스(다이메틸아미노)타이타늄의 제조 Preparation Example 4 Preparation of N, N' -bis ( P, P'-diisopropylthiophosphinyl) -1,2-phenylenediamineyl bis (dimethylamino) titanium

Figure 112008037459202-PAT00011
Figure 112008037459202-PAT00011

질소분위기 하에서 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-1,2-페닐렌다이아민 (202.3 mg, 0.5 mmol)을 벤젠 (5 mL)에 녹인 후 TiCl(NMe2)3 (500 ㎕, 0.5 mmol, 1.0 M solution in benzene)을 넣어주고 30분간 상온에서 교반하였다. 감압 조건에서 벤젠을 제거하여, 상기 표제화합물을 흰색 고체 (263 mg, 98 %)로 얻었다.In a nitrogen atmosphere, N, N' -bis ( P, P'-diisopropylthiophosphinyl) -1,2-phenylenediamine (202.3 mg, 0.5 mmol) was dissolved in benzene (5 mL), followed by TiCl ( NMe 2 ) 3 (500 μl, 0.5 mmol, 1.0 M solution in benzene) was added thereto, followed by stirring at room temperature for 30 minutes. Benzene was removed under reduced pressure to give the title compound as a white solid (263 mg, 98%).

1H NMR (500 MHz, C6D6, 25 ℃) δ 6.90-6.86 (m, 2H), 6.78 (m, 2H), 2.38-2.31 (m, 4H), 1.15 (dd, J = 11.5, 6.5 Hz, 12H), 1.05 (dd, J = 11.5, 6.5 Hz, 12H). 1 H NMR (500 MHz, C 6 D 6 , 25 ° C) δ 6.90-6.86 (m, 2H), 6.78 (m, 2H), 2.38-2.31 (m, 4H), 1.15 (dd, J = 11.5, 6.5 Hz, 12H), 1.05 (dd, J = 11.5, 6.5 Hz, 12H).

제조예 5. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)타이타늄의 제조Preparation Example 5 Preparation of N, N′ -bis ( P, P′-Diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamineyl bis (dimethylamino) titanium

Figure 112008037459202-PAT00012
Figure 112008037459202-PAT00012

질소분위기 하에서 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (199.2 mg, 0.5 mmol)을 벤젠 (5 mL)에 녹인 후 TiCl(NMe2)3 (500 ㎕, 0.5 mmol, 1.0 M solution in benzene)을 넣어주고 30분간 상온에서 교반하였다. 감압 조건에서 벤젠을 제거하여, 상기 표제화합물을 흰색 고체 (255 mg, 96 %)로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (199.2 mg, 0.5 mmol) under nitrogen atmosphere After dissolving in TiCl (NMe 2 ) 3 (500 μl, 0.5 mmol, 1.0 M solution in benzene) was added and stirred at room temperature for 30 minutes. Benzene was removed under reduced pressure to give the title compound as a white solid (255 mg, 96%).

1H NMR (500 MHz, C6D6, 25 ℃) δ 3.34 (d, J = 14.0 Hz, 4H), 3.11 (s, 12H), 2.01 (septet, J = 7.0 Hz, 4H), 1.16 (d, J = 7.0 Hz, 6H), 1.13 (dd, J = 7.0, 1.5 Hz, 12H), 1.11 (s, 6H), 1.09 (d, J = 7.0 Hz, 6H). 1 H NMR (500 MHz, C 6 D 6 , 25 ° C) δ 3.34 (d, J = 14.0 Hz, 4H), 3.11 (s, 12H), 2.01 (septet, J = 7.0 Hz, 4H), 1.16 (d, J = 7.0 Hz, 6H), 1.13 (dd, J = 7.0 , 1.5 Hz, 12H), 1.11 (s, 6H), 1.09 (d, J = 7.0 Hz, 6H).

제조예 6. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,3-다이메틸-2,3-부탄다이아민일 비스(다이메틸아미노)지르코늄의 제조 Preparation Example 6 Preparation of N, N′ -bis ( P, P′-Diisopropylthiophosphinyl) -2,3-dimethyl-2,3-butanediamineyl bis (dimethylamino) zirconium

Figure 112008037459202-PAT00013
Figure 112008037459202-PAT00013

질소분위기 하에서 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,3-다이메틸-2,3-부탄다이아민 (206.3 mg, 0.5 mmol)을 벤젠 (5 mL)에 녹인 후 Zr(NMe2)4 (500 ㎕, 0.5 mmol, 1.0 M solution in benzene)을 넣어주고 30분간 상온에서 교반하였다. 감압 조건에서 벤젠을 제거하여, 상기 표제화합물을 흰색 고체 (304 mg, 92 %)로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,3-dimethyl-2,3-butanediamine (206.3 mg, 0.5 mmol) under nitrogen atmosphere ) Was dissolved in Zr (NMe 2 ) 4 (500 μl, 0.5 mmol, 1.0 M solution in benzene) and stirred at room temperature for 30 minutes. Benzene was removed under reduced pressure to give the title compound as a white solid (304 mg, 92%).

1H NMR (500 MHz, C6D6, 25 ℃) δ 3.16 (s, 12H), 2.12 (septet, J = 7.0 Hz, 4H), 1.31 (td, J = 7.0, 17.5 Hz, 12H), 1.24 (s, 6H), 1.07-1.01 (m, 12H), 0.94 (s, 6H). OneH NMR (500 MHz, C6D6, 25 ℃) δ 3.16 (s, 12H), 2.12 (septet,J = 7.0 Hz, 4H), 1.31 (td,J = 7.0, 17.5 Hz, 12H), 1.24 (s, 6H), 1.07-1.01 (m, 12H), 0.94 (s, 6H).

제조예 7. N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄의 제조Preparation Example 7 Preparation of N, N' -bis ( P, P'-Diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamineyl bis (dimethylamino) zirconium

Figure 112008037459202-PAT00014
Figure 112008037459202-PAT00014

질소분위기 하에서 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (199.2 mg, 0.5 mmol)을 벤젠 (5 mL)에 녹인 후 Zr(NMe2)4 (500 ㎕, 0.5 mmol, 1.0 M solution in benzene)을 넣어주고 30분간 상온에서 교반하였다. 감압 조건에서 벤젠을 제거하여, 상기 표제화합물을 흰색 고체 (276 mg, 96 %)로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (199.2 mg, 0.5 mmol) under nitrogen atmosphere ) Was dissolved in Zr (NMe 2 ) 4 (500 μl, 0.5 mmol, 1.0 M solution in benzene) and stirred at room temperature for 30 minutes. Benzene was removed under reduced pressure to give the title compound as a white solid (276 mg, 96%).

1H NMR (500 MHz, C6D6, 25 ℃) δ 3.11 (s, 12H), 2.69 (d, J = 10.0 Hz, 4H), 1.99 (septet, J = 7.25 Hz, 4H), 1.16 (d, J = 7.0 Hz, 6H), 1.13 (dd, J = 7.0, 1.5 Hz, 12H), 1.09 (d, J = 7.0 Hz, 6H), 0.89 (s, 6H). 1 H NMR (500 MHz, C 6 D 6 , 25 ° C) δ 3.11 (s, 12H), 2.69 (d, J = 10.0 Hz, 4H), 1.99 (septet, J = 7.25 Hz, 4H), 1.16 (d, J = 7.0 Hz, 6H), 1.13 (dd, J = 7.0 , 1.5 Hz, 12H), 1.09 (d, J = 7.0 Hz, 6H), 0.89 (s, 6H).

[실시예] 고리형 이민 화합물의 합성EXAMPLES Synthesis of Cyclic Imine Compound

하기 실시예 1 내지 9에서는, 4B족 금속화합물과 리간드를 투입하여 인-시츄 (in-situ)로 제조된 촉매 하에서 고리형 이민 화합물을 합성한 예이다.In Examples 1 to 9 below, a group 4B metal compound and a ligand were added to synthesize an cyclic imine compound under a catalyst prepared in-situ.

실시예 1. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 1. Preparation of 3,4-dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00015
Figure 112008037459202-PAT00015

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 1.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 After confirming the ligand exchange reaction in the NMR spectrum, 5-phenyl-4-pentynyl-1-amine (65.2 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) were added thereto and heated at 75 ° C. for 1.5 hours. The title compound was obtained in 95% yield in 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 2. 2-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 2. Preparation of 2-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00016
Figure 112008037459202-PAT00016

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 1-메틸-4-노니릴-1-아민 (74.0 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 2.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 98% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 After confirming the ligand exchange reaction in the NMR spectrum, 1-methyl-4-nonyryl-1-amine (74.0 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 2.5 hours to obtain the title compound in 98% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 4.04-3.99 (m, 1H, CHN), 2.57-2.50 (m, 1H, CH 2C=N), 2.45-2.40 (m, 1H, CH 2C=N), 2.30 (t, J = 7.75 Hz, N=CCH 2), 2.10-2.03 (m, 1H, NCHCH 2), 1.60-1.54 (m, 2H, CCH2CH 2CH2), 1.39-1.28 (m, 5H, CCH2CH2CH 2CH 2, NCHCH 2), 1.27 (d, J = 7.0 Hz, 3H, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 4.04-3.99 (m, 1H, C H N), 2.57-2.50 (m, 1H, C H 2 C = N), 2.45-2.40 (m, 1H, C H 2 C = N), 2.30 (t, J = 7.75 Hz, N = CC H 2 ), 2.10-2.03 (m, 1H, NCHC H 2 ), 1.60-1.54 (m, 2H, CCH 2 C H 2 CH 2 ), 1.39-1.28 (m, 5H, CCH 2 CH 2 C H 2 C H 2 , NCHC H 2 ), 1.27 (d, J = 7.0 Hz, 3H, CHC H 3 ), 0.89 (t, J = 7.0 Hz, 3H, CH 2 C H 3 ).

실시예 3. 4-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 3. Preparation of 4-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00017
Figure 112008037459202-PAT00017

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6) 과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 3-메틸-4-노니릴-1-아민 (73.56 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 2.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 93% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 After confirming the ligand exchange reaction in the NMR spectrum, 3-methyl-4-nonyryl-1-amine (73.56 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added thereto and heated at 75 ° C. for 2.5 hours. The title compound was obtained in 93% yield in 1 NMR spectrum.

1H NMR (CDCl3, 400 MHz, 25 ℃) δ 3.82-3.76 (m, 1H, CH 2N), 3.66-3.59 (m, 1H, CH 2N), 2.78-2.68 (m, 1H, CHC=N), 2.35-2.18 (m, 2H, N=CCH 2), 2.15-2.07 (m, 1H, NCH2CH 2), 1.67-1.56 (m, 2H, NCH CH 2), 1.48-1.41 (m, 1H, NCH2CH 2), 1.32 (br m, 2H, CCH2CH 2 CH2CH2), 1.22 (td, J = 5.02 Hz, 1.09 Hz, 2H, CCH2CH2 CH 2 CH2), 1.17 (td, J = 5.58 Hz, 1.03 Hz, 2H, CCH2CH2 CH2CH 2), 1.11 (dd, J = 7.13 Hz, J = 1.34 Hz, 3H, CHCH 3), 0.89 (t, J = 6.10 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 400 MHz, 25 ° C) δ 3.82-3.76 (m, 1H, C H 2 N), 3.66-3.59 (m, 1H, C H 2 N), 2.78-2.68 (m, 1H, C H C = N), 2.35-2.18 (m, 2H , N = CC H 2 ), 2.15-2.07 (m, 1H, NCH 2 C H 2 ), 1.67-1.56 (m, 2H, NCH C H 2 ), 1.48-1.41 (m, 1H, NCH 2 C H 2 ), 1.32 (br m, 2H, CCH 2 C H 2 CH 2 CH 2 ), 1.22 (td, J = 5.02 Hz, 1.09 Hz, 2H, CCH 2 CH 2 C H 2 CH 2 ), 1.17 (td, J = 5.58 Hz, 1.03 Hz, 2H, CCH 2 CH 2 CH 2 C H 2 ), 1.11 (dd, J = 7.13 Hz, J = 1.34 Hz, 3H, CHC H 3 ), 0.89 (t, J = 6.10 Hz, 3H, CH 2 C H 3 ).

실시예 4. 4-벤질옥시-3,3,5-트라이에틸-3,4-다이하이드로-2H-피롤의 제조 Example 4 Preparation of 4-benzyloxy-3,3,5-triethyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00018
Figure 112008037459202-PAT00018

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6) 과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 3-벤질옥시-2,2-다이메틸-5-트라이메틸실릴-4-펜티닐-1-아민(124.24 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 11 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 96% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 After confirming ligand exchange reaction in NMR spectrum, 3-benzyloxy-2,2-dimethyl-5-trimethylsilyl-4-pentynyl-1-amine (124.24 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 11 hours to obtain the title compound in 96% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.38 (d, 2H, J = 4.0 Hz, Ph), 7.34-7.31 (m, 1H, Ph), 4.75 (d, J = 12.0 Hz, 1H, CH 2Ph), 4.60 (d, J = 12.0 Hz, 1H, CH 2Ph), 3.98 (s, 1H, CHOBn), 3.55 (d, J = 14.5 Hz, 1H, CH 2N), 3.37 (d, J = 14.5 Hz, 1H, CH 2N), 2.03 (s, 3H, CCH 3), 1.17 (s, 3H, C(CH 3)2), 1.03 (s, 3H, C(CH 3)2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.38 (d, 2H, J = 4.0 Hz, Ph), 7.34-7.31 (m, 1H, Ph), 4.75 (d, J = 12.0 Hz, 1H, C H 2 Ph), 4.60 (d, J = 12.0 Hz , 1H, C H 2 Ph), 3.98 (s, 1H, C H OBn), 3.55 (d, J = 14.5 Hz, 1H, C H 2 N), 3.37 (d, J = 14.5 Hz, 1H, C H 2 N), 2.03 (s, 3H, CC H 3 ), 1.17 (s, 3H, C (C H 3 ) 2 ), 1.03 (s, 3H, C (C H 3 ) 2 ).

실시예 5. 6-펜틸-2,3,4,5-테트라하이드로-피리딘의 제조 Example 5. Preparation of 6-pentyl-2,3,4,5-tetrahydro-pyridine

Figure 112008037459202-PAT00019
Figure 112008037459202-PAT00019

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 5-데시닐-1-아민 (73.5 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 5.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다.Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 Confirm the ligand exchange reaction in the NMR spectrum, and then 5-decynyl-1-amine (73.5 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 5.5 hours to obtain the title compound in 95% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 3.48 (t, J = 6.5 Hz, 2H, CH 2N), 2.08-2.03 (m, 4H, CH 2C=N, N=CCH 2), 1.62-1.57 (m, 2H, CH 2CH2C=N), 1.51-1.43 (m, 4H, CH 2CH2N, CCH2CH 2), 1.28-1.21 (m, 4H, CH 2CH 2CH3), 0.87 (t, J = 6.75 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 3.48 (t, J = 6.5 Hz, 2H, C H 2 N), 2.08-2.03 (m, 4H, C H 2 C = N, N = CC H 2 ), 1.62-1.57 (m, 2H, C H 2 CH 2 C = N), 1.51-1.43 (m, 4H, C H 2 CH 2 N, CCH 2 C H 2 ), 1.28-1.21 (m, 4H, C H 2 C H 2 CH 3 ), 0.87 (t , J = 6.75 Hz, 3H, CH 2 C H 3 ).

실시예 6. 5-메틸-6-펜틸-2,3,4,5-테트라하이드로-피리딘의 제조 Example 6. Preparation of 5-methyl-6-pentyl-2,3,4,5-tetrahydro-pyridine

Figure 112008037459202-PAT00020
Figure 112008037459202-PAT00020

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6) 과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 4-메틸-데크-5-인일아민 (77.43㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 10 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 92% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 After confirming ligand exchange reaction in NMR spectrum, 4-methyl-deck-5-ynylamine (77.43 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 10 hours to obtain the title compound in 92% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 3.58-3.50 (m, 2H, CH 2N), 2.26-2.16 (m, 3H, CH 2C=N, N=CCHCH3), 1.80-1.74 (m, 1H, CH 2CHC=N), 1.66-1.59 (m, 1H, CH 2CH-C=N), 1.56-1.46 (m, 3H, CH 2CH2C=N, NCH2CH 2), 1.45-1.40 (m, 1H, NCH2CH 2), 1.35-1.25 (m, 4H, CH 2CH 2CH3), 1.13 (d, J = 7.5 Hz, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 3.58-3.50 (m, 2H, C H 2 N), 2.26-2.16 (m, 3H, C H 2 C = N, N = CC H CH 3 ), 1.80-1.74 (m, 1H, C H 2 CHC = N), 1.66-1.59 (m, 1H, C H 2 CH-C = N), 1.56-1.46 (m, 3H, C H 2 CH 2 C = N, NCH 2 C H 2 ), 1.45-1.40 (m , 1H, NCH 2 C H 2 ), 1.35-1.25 (m, 4H, C H 2 C H 2 CH 3 ), 1.13 (d, J = 7.5 Hz, CHC H 3 ), 0.89 (t, J = 7.0 Hz , 3H, CH 2 C H 3 ).

실시예 7. 7-벤질-3,4,5,6-테트라하이드로-2H-아제핀의 제조 Example 7. Preparation of 7-benzyl-3,4,5,6-tetrahydro-2 H -azepine

Figure 112008037459202-PAT00021
Figure 112008037459202-PAT00021

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 Zr(NMe2)4 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 2,2-다이메틸-7-페닐-6-헵티닐-1-아민 (92.12 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 100 ℃에서 7시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 93% 수득률로 얻었다. Zr (NMe 2 ) 4 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 Verify the ligand exchange reaction in the NMR spectrum, then 2,2-dimethyl-7-phenyl-6-heptinyl-1-amine (92.12 μL, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 100 ° C. for 7 hours to obtain the title compound in 93% yield in 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.30-7.25 (m, 4H, Ph), 7.22-7.20 (m, 1H, Ph), 3.55 (s, 2H, CH 2Ph), 3.40 (s, 2H, CH 2N), 2.24 (t, J = 5.75 Hz, 2H, CH 2C=N), 1.40 (t, J = 6.0 Hz, 2H, (CH3)2CCH 2), 1.20-1.14 (m, 2H, CH2 CH 2CH2), 0.88 (s, 6H, (CH 3)2C). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.30-7.25 (m, 4H, Ph), 7.22-7.20 (m, 1H, Ph), 3.55 (s, 2H, C H 2 Ph), 3.40 (s, 2H, C H 2 N), 2.24 (t, J = 5.75 Hz, 2H, C H 2 C = N), 1.40 (t, J = 6.0 Hz, 2H, (CH 3 ) 2 CC H 2 ), 1.20-1.14 (m, 2H, CH 2 CH 2 CH 2 ), 0.88 (s, 6H, (C H 3 ) 2 C).

실시예 8. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 8. Preparation of 3,4-Dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00022
Figure 112008037459202-PAT00022

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 TiCl(NMe2)3 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온(20 ℃)에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다. TiCl (NMe 2 ) 3 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by room temperature (20 ° C). Stirred for 10 minutes. 1 Confirm the ligand exchange reaction in the NMR spectrum, and then read 5-phenyl-4-pentynyl-1-amine (65.2 μl, 0.4 mmol) and para xylene. (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 5 hours to obtain the title compound in 95% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 9. 2-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 9. Preparation of 2-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00023
Figure 112008037459202-PAT00023

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 TiCl(NMe2)3 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)과 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민 (7.97 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 실온에서 10분간 교반하였다. 1NMR 스펙트럼에서 리간드 교환반응을 확인한 후 1-메틸-4-노니릴-1-아민 (74.0 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 125 ℃에서 6.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 92% 수득률로 얻었다. TiCl (NMe 2 ) 3 (20 μl, 0.02 mmol, 1.0 M solution in benzene- d 6 ) and N, N′ -bis ( P ) were placed in a J. Young NMR tube in an argon-filled glove box. , P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3-propanediamine (7.97 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added and 10 minutes at room temperature. Stirred. 1 After confirming the ligand exchange reaction in the NMR spectrum, 1-methyl-4-nonyryl-1-amine (74.0 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) were added thereto, and heated at 125 ° C. for 6.5 hours. The title compound was obtained in 92% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 4.04-3.99 (m, 1H, CHN), 2.57-2.50 (m, 1H, CH 2C=N), 2.45-2.40 (m, 1H, CH 2C=N), 2.30 (t, J = 7.75 Hz, N=CCH 2), 2.10-2.03 (m, 1H, NCHCH 2), 1.60-1.54 (m, 2H, CCH2CH 2CH2), 1.39-1.28 (m, 5H, CCH2CH2CH 2CH 2, NCHCH 2), 1.27 (d, J = 7.0 Hz, 3H, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 4.04-3.99 (m, 1H, C H N), 2.57-2.50 (m, 1H, C H 2 C = N), 2.45-2.40 (m, 1H, C H 2 C = N), 2.30 (t, J = 7.75 Hz, N = CC H 2 ), 2.10-2.03 (m, 1H, NCHC H 2 ), 1.60-1.54 (m, 2H, CCH 2 C H 2 CH 2 ), 1.39-1.28 (m, 5H, CCH 2 CH 2 C H 2 C H 2 , NCHC H 2 ), 1.27 (d, J = 7.0 Hz, 3H, CHC H 3 ), 0.89 (t, J = 7.0 Hz, 3H, CH 2 C H 3 ).

하기 실시예 10 및 11에서는, 타이타늄-아미노 화합물을 촉매로 사용하여 고리형 이민 화합물을 합성한 예이다.In Examples 10 and 11 below, a cyclic imine compound was synthesized using a titanium-amino compound as a catalyst.

실시예 10. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 10 Preparation of 3,4-dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00024
Figure 112008037459202-PAT00024

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 TiCl(NMe2)3 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)을 넣은 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 60 ℃에서 1 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 96% 수득률로 얻었다. TiCl (NMe 2 ) 3 (20 μl, 0.02 mmol, 1.0 M solution in benzene -d 6 ) was added to J. Young NMR tube in argon-filled glove box. Pentynyl-1-amine (65.2 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) were added and heated at 60 ° C. for 1 hour to obtain the title compound in 96% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 11. 2-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 11. Preparation of 2-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00025
Figure 112008037459202-PAT00025

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 TiCl(NMe2)3 (20 ㎕, 0.02 mmol, 1.0 M solution in benzene-d 6)을 넣은 후 1-메틸-4-노니릴-1-아민 (74.0 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 17 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 91% 수득률로 얻었다. TiCl (NMe 2 ) 3 (20 μl, 0.02 mmol, 1.0 M solution in benzene -d 6 ) was added to J. Young NMR tube in an argon filled glove box, followed by 1-methyl-4- Noniryl-1-amine (74.0 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) were added and heated at 75 ° C. for 17 hours to obtain the title compound in 91% yield in 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 4.04-3.99 (m, 1H, CHN), 2.57-2.50 (m, 1H, CH 2C=N), 2.45-2.40 (m, 1H, CH 2C=N), 2.30 (t, J = 7.75 Hz, N=CCH 2), 2.10-2.03 (m, 1H, NCHCH 2), 1.60-1.54 (m, 2H, CCH2CH 2CH2), 1.39-1.28 (m, 5H, CCH2CH2CH 2CH 2, NCHCH 2), 1.27 (d, J = 7.0 Hz, 3H, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 4.04-3.99 (m, 1H, C H N), 2.57-2.50 (m, 1H, C H 2 C = N), 2.45-2.40 (m, 1H, C H 2 C = N), 2.30 (t, J = 7.75 Hz, N = CC H 2 ), 2.10-2.03 (m, 1H, NCHC H 2 ), 1.60-1.54 (m, 2H, CCH 2 C H 2 CH 2 ), 1.39-1.28 (m, 5H, CCH 2 CH 2 C H 2 C H 2 , NCHC H 2 ), 1.27 (d, J = 7.0 Hz, 3H, CHC H 3 ), 0.89 (t, J = 7.0 Hz, 3H, CH 2 C H 3 ).

하기 실시예 12 내지 22에서는, 상기 제조예에서 합성한 4B족 금속착물을 촉매로 사용하여 고리형 이민 화합물을 합성한 예이다.In Examples 12 to 22 below, the cyclic imine compound was synthesized using the Group 4B metal complex synthesized in Preparation Example as a catalyst.

실시예 12. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 12. Preparation of 3,4-Dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00026
Figure 112008037459202-PAT00026

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-1,2-페닐렌다이아민일 비스(다이메틸아미노)타이타늄 (상기 제조예 4) (10.7 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 125 ℃에서 8 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -1,2-phenylenediamineyl bis (in J. Young NMR tube) in a glove box filled with argon. Dimethylamino) titanium (Preparation Example 4) (10.7 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added, followed by 5-phenyl-4-pentynyl-1-amine (65.2 μl, 0.4 mmol). Para xylene (10 μl, 0.08 mmol) was added and heated at 125 ° C. for 8 hours to obtain the title compound in 95% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 13. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 13. Preparation of 3,4-dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00027
Figure 112008037459202-PAT00027

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)타이타늄 (상기 제조예 5) (10.6 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 60 ℃에서 11 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) titanium (Preparation Example 5 above) (10.6 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 5-phenyl-4-pentynyl-1-amine (65.2 Μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 60 ° C. for 11 hours to obtain the title compound in 95% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 14. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 14 Preparation of 3,4-Dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00028
Figure 112008037459202-PAT00028

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,3-다이메틸-2,3-부탄다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 6) (13.2 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 60 ℃에서 8 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 91% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,3-dimethyl-2,3 in a J. Young NMR tube in an argon filled glove box Butanediamineyl bis (dimethylamino) zirconium (Preparation Example 6) (13.2 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 5-phenyl-4-pentynyl-1-amine (65.2 Μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 60 ° C. for 8 hours to obtain the title compound in 91% yield in 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 15. 3,4-다이하이드로-5-(페닐메틸)-2H-피롤의 제조 Example 15. Preparation of 3,4-Dihydro-5- (phenylmethyl) -2 H -pyrrole

Figure 112008037459202-PAT00029
Figure 112008037459202-PAT00029

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 5-페닐-4-펜티닐-1-아민 (65.2 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 60 ℃에서 1.5 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 95% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 5-phenyl-4-pentynyl-1-amine (65.2 Μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 60 ° C. for 1.5 hours to obtain the title compound in 95% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, CH 2NH2), 3.69 (s, 2H, CH 2Ph), 2.40 (t, J = 8.0 Hz, 2H, CH2CH2CH 2), 1.84 (quintet, J = 8.0 Hz, 2H, CH2CH 2CH2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.33-7.30 (m, 2H, Ph), 7.25-7.22 (m, 3H, Ph), 3.84 (t, J = 6.0 Hz, 2H, C H 2 NH 2 ), 3.69 (s, 2H, C H 2 Ph ), 2.40 (t, J = 8.0 Hz, 2H, CH 2 CH 2 C H 2 ), 1.84 (quintet, J = 8.0 Hz, 2H, CH 2 C H 2 CH 2 ).

실시예 16. 2-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 16 Preparation of 2-methyl-5-pentyl-3,4-dihydro- 2H -pyrrole

Figure 112008037459202-PAT00030
Figure 112008037459202-PAT00030

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 1-메틸-4-노니릴-1-아민 (74.0 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 3 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 94% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 1-methyl-4-nonyryl-1-amine (74.0 Μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 3 hours to obtain the title compound in 94% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 4.04-3.99 (m, 1H, CHN), 2.57-2.50 (m, 1H, CH 2C=N), 2.45-2.40 (m, 1H, CH 2C=N), 2.30 (t, J = 7.75 Hz, N=CCH 2), 2.10-2.03 (m, 1H, NCHCH 2), 1.60-1.54 (m, 2H, CCH2CH 2CH2), 1.39-1.28 (m, 5H, CCH2CH2CH 2CH 2, NCHCH 2), 1.27 (d, J = 7.0 Hz, 3H, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 4.04-3.99 (m, 1H, C H N), 2.57-2.50 (m, 1H, C H 2 C = N), 2.45-2.40 (m, 1H, C H 2 C = N), 2.30 (t, J = 7.75 Hz, N = CC H 2 ), 2.10-2.03 (m, 1H, NCHC H 2 ), 1.60-1.54 (m, 2H, CCH 2 C H 2 CH 2 ), 1.39-1.28 (m, 5H, CCH 2 CH 2 C H 2 C H 2 , NCHC H 2 ), 1.27 (d, J = 7.0 Hz, 3H, CHC H 3 ), 0.89 (t, J = 7.0 Hz, 3H, CH 2 C H 3 ).

실시예 17. 4-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 17. Preparation of 4-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00031
Figure 112008037459202-PAT00031

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 3-메틸-4-노니릴-1-아민 (73.56 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 4 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 96% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 3-methyl-4-nonyryl-1-amine (73.56 Μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) were added and heated at 75 ° C. for 4 hours to obtain the title compound in 96% yield in 1 NMR spectrum.

1H NMR (CDCl3, 400 MHz, 25 ℃) δ 3.82-3.76 (m, 1H, CH 2N), 3.66-3.59 (m, 1H, CH 2N), 2.78-2.68 (m, 1H, CHC=N), 2.35-2.18 (m, 2H, N=CCH 2), 2.15-2.07 (m, 1H, NCH2CH 2), 1.67-1.56 (m, 2H, NCH CH 2), 1.48-1.41 (m, 1H, NCH2CH 2), 1.32 (br m, 2H, CCH2CH 2 CH2CH2), 1.22 (td, J = 5.02 Hz, 1.09 Hz, 2H, CCH2CH2 CH 2 CH2), 1.17 (td, J = 5.58 Hz, 1.03 Hz, 2H, CCH2CH2 CH2CH 2), 1.11 (dd, J = 7.13 Hz, J = 1.34 Hz, 3H, CHCH 3), 0.89 (t, J = 6.10 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 400 MHz, 25 ° C) δ 3.82-3.76 (m, 1H, C H 2 N), 3.66-3.59 (m, 1H, C H 2 N), 2.78-2.68 (m, 1H, C H C = N), 2.35-2.18 (m, 2H , N = CC H 2 ), 2.15-2.07 (m, 1H, NCH 2 C H 2 ), 1.67-1.56 (m, 2H, NCH C H 2 ), 1.48-1.41 (m, 1H, NCH 2 C H 2 ), 1.32 (br m, 2H, CCH 2 C H 2 CH 2 CH 2 ), 1.22 (td, J = 5.02 Hz, 1.09 Hz, 2H, CCH 2 CH 2 C H 2 CH 2 ), 1.17 (td, J = 5.58 Hz, 1.03 Hz, 2H, CCH 2 CH 2 CH 2 C H 2 ), 1.11 (dd, J = 7.13 Hz, J = 1.34 Hz, 3H, CHC H 3 ), 0.89 (t, J = 6.10 Hz, 3H, CH 2 C H 3 ).

실시예 18. 4-벤질옥시-3,3,5-트라이에틸-3,4-다이하이드로-2H-피롤의 제조 Example 18 Preparation of 4-benzyloxy-3,3,5-triethyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00032
Figure 112008037459202-PAT00032

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 3-벤질옥시-2,2-다이메틸-5-트라이메틸실릴-4-펜티닐-1-아민(124.24 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 13 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 96% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 3-benzyloxy-2,2-dimethyl-5- Trimethylsilyl-4-pentynyl-1-amine (124.24 μl, 0.4 mmol) with para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 13 hours to obtain the title compound in 96% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.38 (d, 2H, J = 4.0 Hz, Ph), 7.34-7.31 (m, 1H, Ph), 4.75 (d, J = 12.0 Hz, 1H, CH 2Ph), 4.60 (d, J = 12.0 Hz, 1H, CH 2Ph), 3.98 (s, 1H, CHOBn), 3.55 (d, J = 14.5 Hz, 1H, CH 2N), 3.37 (d, J = 14.5 Hz, 1H, CH 2N), 2.03 (s, 3H, CCH 3), 1.17 (s, 3H, C(CH 3)2), 1.03 (s, 3H, C(CH 3)2). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.38 (d, 2H, J = 4.0 Hz, Ph), 7.34-7.31 (m, 1H, Ph), 4.75 (d, J = 12.0 Hz, 1H, C H 2 Ph), 4.60 (d, J = 12.0 Hz , 1H, C H 2 Ph), 3.98 (s, 1H, C H OBn), 3.55 (d, J = 14.5 Hz, 1H, C H 2 N), 3.37 (d, J = 14.5 Hz, 1H, C H 2 N), 2.03 (s, 3H, CC H 3 ), 1.17 (s, 3H, C (C H 3 ) 2 ), 1.03 (s, 3H, C (C H 3 ) 2 ).

실시예 19. 6-펜틸-2,3,4,5-테트라하이드로-피리딘의 제조 Example 19. Preparation of 6-pentyl-2,3,4,5-tetrahydro-pyridine

Figure 112008037459202-PAT00033
Figure 112008037459202-PAT00033

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 5-데시닐-1-아민 (73.5 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 7 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 96% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 5-decynyl-1-amine (73.5 μl, 0.4 mmol). ) And para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 7 hours to obtain the title compound in 96% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 3.48 (t, J = 6.5 Hz, 2H, CH 2N), 2.08-2.03 (m, 4H, CH 2C=N, N=CCH 2), 1.62-1.57 (m, 2H, CH 2CH2C=N), 1.51-1.43 (m, 4H, CH 2CH2N, CCH2CH 2), 1.28-1.21 (m, 4H, CH 2CH 2CH3), 0.87 (t, J = 6.75 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 3.48 (t, J = 6.5 Hz, 2H, C H 2 N), 2.08-2.03 (m, 4H, C H 2 C = N, N = CC H 2 ), 1.62-1.57 (m, 2H, C H 2 CH 2 C = N), 1.51-1.43 (m, 4H, C H 2 CH 2 N, CCH 2 C H 2 ), 1.28-1.21 (m, 4H, C H 2 C H 2 CH 3 ), 0.87 (t , J = 6.75 Hz, 3H, CH 2 C H 3 ).

실시예 20. 5-메틸-6-펜틸-2,3,4,5-테트라하이드로-피리딘의 제조 Example 20. Preparation of 5-methyl-6-pentyl-2,3,4,5-tetrahydro-pyridine

Figure 112008037459202-PAT00034
Figure 112008037459202-PAT00034

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 4-메틸-데크-5-인일아민 (77.43㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 10 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 92% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added followed by 4-methyl-deck-5-ynylamine (77.43 μl, 0.4 mmol) and para xylene (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 10 hours to obtain the title compound in 92% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 3.58-3.50 (m, 2H, CH 2N), 2.26-2.16 (m, 3H, CH 2C=N, N=CCHCH3), 1.80-1.74 (m, 1H, CH 2CHC=N), 1.66-1.59 (m, 1H, CH 2CH-C=N), 1.56-1.46 (m, 3H, CH 2CH2C=N, NCH2CH 2), 1.45-1.40 (m, 1H, NCH2CH 2), 1.35-1.25 (m, 4H, CH 2CH 2CH3), 1.13 (d, J = 7.5 Hz, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 3.58-3.50 (m, 2H, C H 2 N), 2.26-2.16 (m, 3H, C H 2 C = N, N = CC H CH 3 ), 1.80-1.74 (m, 1H, C H 2 CHC = N), 1.66-1.59 (m, 1H, C H 2 CH-C = N), 1.56-1.46 (m, 3H, C H 2 CH 2 C = N, NCH 2 C H 2 ), 1.45-1.40 (m , 1H, NCH 2 C H 2 ), 1.35-1.25 (m, 4H, C H 2 C H 2 CH 3 ), 1.13 (d, J = 7.5 Hz, CHC H 3 ), 0.89 (t, J = 7.0 Hz , 3H, CH 2 C H 3 ).

실시예 21. 7-벤질-3,4,5,6-테트라하이드로-2H-아제핀의 제조 Example 21. Preparation of 7-benzyl-3,4,5,6-tetrahydro-2 H -azepine

Figure 112008037459202-PAT00035
Figure 112008037459202-PAT00035

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아민일 비스(다이메틸아미노)지르코늄 (상기 제조예 7) (11.5 mg, 0.02 mmol)과 벤젠-d 6 (0.4 mL)을 넣은 후 2,2-다이메틸-7-페닐-6-헵티닐-1-아민 (92.12 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 100 ℃에서 8시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 94% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediamineyl bis (dimethylamino) zirconium (Preparation Example 7) (11.5 mg, 0.02 mmol) and benzene- d 6 (0.4 mL) were added, followed by 2,2-dimethyl-7-phenyl-6-hep Tinyl-1-amine (92.12 μl, 0.4 mmol) with para xylene (10 μl, 0.08 mmol) was added and heated at 100 ° C. for 8 hours to obtain the title compound in 94% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 7.30-7.25 (m, 4H, Ph), 7.22-7.20 (m, 1H, Ph), 3.55 (s, 2H, CH 2Ph), 3.40 (s, 2H, CH 2N), 2.24 (t, J = 5.75 Hz, 2H, CH 2C=N), 1.40 (t, J = 6.0 Hz, 2H, (CH3)2CCH 2), 1.20-1.14 (m, 2H, CH2 CH 2CH2), 0.88 (s, 6H, (CH 3)2C). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 7.30-7.25 (m, 4H, Ph), 7.22-7.20 (m, 1H, Ph), 3.55 (s, 2H, C H 2 Ph), 3.40 (s, 2H, C H 2 N), 2.24 (t, J = 5.75 Hz, 2H, C H 2 C = N), 1.40 (t, J = 6.0 Hz, 2H, (CH 3 ) 2 CC H 2 ), 1.20-1.14 (m, 2H, CH 2 CH 2 CH 2 ), 0.88 (s, 6H, (C H 3 ) 2 C).

실시예 22. 2-메틸-5-펜틸-3,4-다이하이드로-2H-피롤의 제조 Example 22. Preparation of 2-methyl-5-pentyl-3,4-dihydro-2 H -pyrrole

Figure 112008037459202-PAT00036
Figure 112008037459202-PAT00036

아르곤으로 채워진 글로브 박스 안에서 제이-영-튜브(J. Young NMR tube)에 N,N'-비스(P,P'-다이아이소프로필싸이오포스피닐)-2,2-다이메틸-1,3-프로판다이아 민일 비스(다이메틸아미노)타이타늄 (상기 제조예 5) (10.6 mg, 0.02 mmol)을 넣은 후 1-메틸-4-노니릴-1-아민 (74.0 ㎕, 0.4 mmol)과 파라 자일렌 (10 ㎕, 0.08 mmol)을 넣고 75 ℃에서 43 시간 가열하여, 상기 표제 화합물을 1NMR 스펙트럼에서 73% 수득률로 얻었다. N, N' -bis ( P, P'-diisopropylthiophosphinyl) -2,2-dimethyl-1,3 in a J. Young NMR tube in an argon-filled glove box Propanediazinyl bis (dimethylamino) titanium (Preparation Example 5) (10.6 mg, 0.02 mmol) was added, followed by 1-methyl-4-nonylyl-1-amine (74.0 μl, 0.4 mmol) and para xylene. (10 μl, 0.08 mmol) was added and heated at 75 ° C. for 43 hours to obtain the title compound in 73% yield on 1 NMR spectrum.

1H NMR (CDCl3, 500 MHz, 25 ℃) δ 4.04-3.99 (m, 1H, CHN), 2.57-2.50 (m, 1H, CH 2C=N), 2.45-2.40 (m, 1H, CH 2C=N), 2.30 (t, J = 7.75 Hz, N=CCH 2), 2.10-2.03 (m, 1H, NCHCH 2), 1.60-1.54 (m, 2H, CCH2CH 2CH2), 1.39-1.28 (m, 5H, CCH2CH2CH 2CH 2, NCHCH 2), 1.27 (d, J = 7.0 Hz, 3H, CHCH 3), 0.89 (t, J = 7.0 Hz, 3H, CH2CH 3). 1 H NMR (CDCl 3 , 500 MHz, 25 ° C) δ 4.04-3.99 (m, 1H, C H N), 2.57-2.50 (m, 1H, C H 2 C = N), 2.45-2.40 (m, 1H, C H 2 C = N), 2.30 (t, J = 7.75 Hz, N = CC H 2 ), 2.10-2.03 (m, 1H, NCHC H 2 ), 1.60-1.54 (m, 2H, CCH 2 C H 2 CH 2 ), 1.39-1.28 (m, 5H, CCH 2 CH 2 C H 2 C H 2 , NCHC H 2 ), 1.27 (d, J = 7.0 Hz, 3H, CHC H 3 ), 0.89 (t, J = 7.0 Hz, 3H, CH 2 C H 3 ).

본 발명에 따른 촉매는 기존에 알려진 넌-메탈로센(non-metallocene) 촉매에 비교하여 리간드의 구조가 간단하여 합성이 용이하다.The catalyst according to the present invention has a simple structure of the ligand compared to the conventionally known non-metallocene catalyst and thus is easy to synthesize.

특히 본 발명에 따른 촉매는 리간드의 구조적 특징으로 인하여 4B족 금속의 선택범위를 확대시킬 수 있음은 물론이고, 분자내 하이드로아미네이션 반응에 적용이 용이하지 않았던 다양한 종류의 아미노알킨 유도체를 기질로서 적용하는 것이 가능하다. 이로써 다양한 구조의 고리형 이민 화합물의 합성이 가능해졌다.In particular, the catalyst according to the present invention can broaden the selection range of the Group 4B metal due to the structural characteristics of the ligand, and apply various kinds of aminoalkyne derivatives, which were not easy to apply to intramolecular hydroamination reactions, as substrates. It is possible to. This enabled the synthesis of cyclic imine compounds of various structures.

또한 이렇게 만들어진 고리 이민 화합물은 생화학적 기본구조 물질인 알칼로이드의 전구체로 사용될 수 있다.In addition, the ring imine compound thus prepared may be used as a precursor of an alkaloid which is a biochemical basic material.

Claims (7)

하기 화학식 2로 표시되는 타이타늄-아미노 화합물인 것을 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매 :Catalyst for intramolecular hydroamination reaction, characterized in that the titanium-amino compound represented by the formula (2): [화학식 2][Formula 2] TiClp(NR2)q TiCl p (NR 2 ) q 상기 화학식 2에서, R은 C1∼C6의 직쇄 또는 분쇄형 알킬기를 나타내고; p는 0 또는 1이고, p+q=4이다.In Chemical Formula 2, R represents a C 1 to C 6 straight or branched alkyl group; p is 0 or 1 and p + q = 4. 하기 화학식 3a, 3b, 또는 3c로 표시되는 4B족 금속착물인 것을 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매 :A catalyst for intramolecular hydroamination reaction, characterized in that the group 4B metal complex represented by the formula 3a, 3b, or 3c:
Figure 112008037459202-PAT00037
Figure 112008037459202-PAT00037
상기 화학식 3a, 3b, 또는 3c에서, X 및 Q는 서로 같거나 다른 것으로서 C1∼C6의 직쇄 또는 분쇄형 알킬기, 페닐기, 또는 벤질기를 나타내고; M은 4B족 금속원자를 나타낸다.In Formulas 3a, 3b, or 3c, X and Q are the same as or different from each other, and represent a C 1 to C 6 straight or pulverized alkyl group, phenyl group, or benzyl group; M represents a Group 4B metal atom.
4B족 금속화합물과, 하기 화학식 4a, 4b, 또는 4c로부터 선택된 리간드로 구성되는 것을 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매 조성물 :A catalyst composition for intramolecular hydroamination reaction, comprising a Group 4B metal compound and a ligand selected from Formulas 4a, 4b, or 4c:
Figure 112008037459202-PAT00038
Figure 112008037459202-PAT00038
상기 화학식 4a, 4b, 또는 4c에서, X 및 Q는 서로 같거나 다른 것으로서 C1∼C6의 직쇄 또는 분쇄형 알킬기, 페닐기, 또는 벤질기를 나타낸다.In Formulas 4a, 4b, or 4c, X and Q are the same as or different from each other, and represent a C 1 to C 6 straight or crushed alkyl group, a phenyl group, or a benzyl group.
제 3 항에 있어서,The method of claim 3, wherein 상기 4B족 금속화합물은 하기 화학식 5로 표시되는 금속화합물로부터 선택된 것을 특징으로 하는 분자내 하이드로아미네이션 반응용 촉매 조성물 :The 4B group metal compound is a catalyst composition for intramolecular hydroamimination reaction, characterized in that selected from the metal compounds represented by the formula (5): [화학식 5][Formula 5] MClm(NR2)n MCl m (NR 2 ) n 상기 화학식 5에서, M은 4B족 금속원자를 나타내고, R은 C1∼C6의 직쇄 또는 분쇄형 알킬기를 나태내고; m은 0 또는 1 내지 4의 정수이고, n+m=4이다.In Formula 5, M represents a Group 4B metal atom, and R represents a C 1 to C 6 straight or pulverized alkyl group; m is 0 or an integer of 1 to 4, and n + m = 4. 상기 청구항 1 내지 4 중에서 선택된 어느 한 항의 촉매의 존재 하에서, 하기 화학식 6으로 표시되는 아미노알킨 유도체를 분자내 하이드로아미네이션 반응시켜 제조하는 것을 특징으로 하는 하기 화학식 1로 표시되는 고리형 이민 화합물의 제조방법:Preparation of the cyclic imine compound represented by the following Chemical Formula 1, characterized in that in the presence of the catalyst of any one of the claims 1 to 4, the amino alkyne derivative represented by the following formula (6) Way: [화학식 6] [Formula 6]
Figure 112008037459202-PAT00039
Figure 112008037459202-PAT00039
[화학식 1][Formula 1]
Figure 112008037459202-PAT00040
Figure 112008037459202-PAT00040
상기 화학식 1 또는 6에서, R1, R2, 및 R3은 서로 같거나 다른 것으로서 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 벤질기, 또는 벤질옥시기를 나타내고; R4는 수소원자, C1∼C6의 직쇄 또는 분쇄형 알킬기, 또는 페닐기를 나타내고; n은 1 내지 3의 정수이다. In Formula 1 or 6, R 1 , R 2 , and R 3 are the same as or different from each other, and represent a hydrogen atom, a C 1 -C 6 straight or crushed alkyl group, benzyl group, or benzyloxy group; R 4 represents a hydrogen atom, a C 1 to C 6 straight or branched alkyl group, or a phenyl group; n is an integer of 1-3.
제 5 항에 있어서,The method of claim 5, wherein 상기 분자내 하이드로아미네이션 반응용매가 탄소수 6 내지 10의 방향족 탄화수소인 것을 특징으로 하는 고리형 이민 화합물의 제조방법.The method for producing a cyclic imine compound, characterized in that the intramolecular hydroamination reaction solvent is an aromatic hydrocarbon having 6 to 10 carbon atoms. 제 5 항에 있어서,The method of claim 5, wherein 상기 분자내 하이드로아미네이션 반응온도가 20 ℃ 내지 150 ℃인 것을 특징으로 하는 고리형 이민 화합물의 제조방법.The method for producing a cyclic imine compound, characterized in that the intramolecular hydro amination reaction temperature is 20 ℃ to 150 ℃.
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