KR101598179B1 - Improved preparing method of oxindole dimers and oxindole dimers made by the same - Google Patents

Improved preparing method of oxindole dimers and oxindole dimers made by the same Download PDF

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KR101598179B1
KR101598179B1 KR1020140001867A KR20140001867A KR101598179B1 KR 101598179 B1 KR101598179 B1 KR 101598179B1 KR 1020140001867 A KR1020140001867 A KR 1020140001867A KR 20140001867 A KR20140001867 A KR 20140001867A KR 101598179 B1 KR101598179 B1 KR 101598179B1
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oxyindole
acetate
cdcl
nmr
mhz
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KR20150081901A (en
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김재녕
이현주
임진우
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전남대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Abstract

본 발명은 옥시인돌 이합체의 제조 방법에 관한 것으로, 보다 상세하게는 3-알킬 치환 옥시인돌 및 산화제를 혼합한 후 환류(reflux) 반응을 통해 옥시인돌 이합체를 제조하는 방법에 관한 것이다.
본 발명은 옥시인돌 이합체의 제조 방법은 3-알킬 치환 옥시인돌의 3번 탄소 간에 단일 결합을 직접적으로 형성시킴으로써 옥시인돌 이합체를 고수율로 제조할 수 있다.The present invention relates to a process for preparing an oxyindole dimer, and more particularly, to a process for preparing an oxyindole duplex through a reflux reaction after mixing a 3-alkyl-substituted oxyindole and an oxidizing agent.
The process of the present invention can produce an oxyindole dimer at a high yield by directly forming a single bond between the carbon number 3 of the 3-alkyl substituted oxyindole.

Description

개선된 옥시인돌 이합체의 제조 방법 및 이에 의하여 제조된 옥시인돌 이합체{Improved preparing method of oxindole dimers and oxindole dimers made by the same}TECHNICAL FIELD The present invention relates to a process for preparing an oxyindole dimer and an oxyindole dimer prepared thereby,

본 발명은 옥시인돌 이합체의 제조 방법 및 이에 의하여 제조된 옥시인돌 이합체에 관한 것으로, 보다 상세하게는 3-알킬 치환 옥시인돌 및 산화제를 혼합한 후 환류(reflux) 반응을 통해 옥시인돌 이합체를 제조하는 옥시인돌 이합체의 제조 방법 및 이에 의하여 제조된 옥시인돌 이합체에 관한 것이다.
The present invention relates to a process for producing an oxyindole dimer and an oxyindole dimer produced thereby, and more particularly to a process for producing an oxyindole duplex by mixing a 3-alkyl-substituted oxyindole and an oxidizing agent and then refluxing A process for producing an oxyindole dimer and an oxyindole dimer produced thereby.

옥시인돌 이합체는 다양한 사이클로트립타민 알칼로이드(Cyclotryptamine Alkaloid)의 합성에 있어 중간체로 사용되어 왔다. 따라서 옥시인돌 이합체를 합성하기 위해 광범위한 연구가 수행되어 왔다. J. Am. Chem. Soc. 1994, 116, 9480-9486.에서 Rodrigo와 그의 동료들은 라디칼 음이온 연쇄 메카니즘(radical anion chain mechanism)을 통해 옥시인돌 음이온을 이합체화하는 것을 보고하였다. 또한 Heterocycles 1982, 19, 2139-2142.에서 Inada와 Morita는 Co(Ⅱ) Schiff's base 복합체를 이용하여 옥시인돌 이합체를 합성하는 것을 발표하였다. Oxyindole dimers have been used as intermediates in the synthesis of various cyclotryptamine alkaloids. Therefore, extensive studies have been conducted to synthesize oxyindole dimers. J. Am. Chem. Soc. In 1994, 116, 9480-9486, Rodrigo and his colleagues reported dimerization of the oxyindole anion via a radical anion chain mechanism. In addition, Hada and Morita in Heterocycles 1982, 19, 2139-2142 have reported the synthesis of oxyindole dimers using Co (Ⅱ) Schiff's base complex.

종래 이와 같이 다양한 직간접적인 옥시인돌 이합체의 제조방법에 대해 보고되고 있지만, 여전히 보다 간이한 방법으로 고수율의 옥시인돌 이합체를 제조하는 방법에 대한 요구가 있다.
Conventionally, various direct or indirect methods for producing oxyindole dimers have been reported. However, there is still a need for a method for producing oxyindole dimers in a high yield by a simpler method.

J. Am. Chem. Soc. 1994, 116, 9480-9486.J. Am. Chem. Soc. 1994, 116, 9480-9486. Heterocycles 1982, 19, 2139-2142.Heterocycles 1982,19, 2139-2142.

본 발명은 개선된 옥시인돌 이합체의 제조 방법 및 이에 의하여 제조된 옥시인돌 이합체를 제공하는 것을 목적으로 한다.
The present invention provides a process for producing an improved oxyindole dimer and an oxyindole duplex produced by the process.

본 발명은 상기와 같은 과제를 해결하기 위하여 The present invention has been made to solve the above problems

화학식 1로 표시되는 3-알킬 치환 옥시인돌을 준비하는 단계; 및 Preparing a 3-alkyl substituted oxyindole represented by the formula (1); And

상기 3-알킬 치환 옥시인돌을 산화제와 유기 용매에 용해시키고 질소 또는 산소 분위기에서 50 내지 150 ℃에서 환류(reflux) 시키면서 반응시키는 단계; 를 포함하는 아래 화학식 2 또는 화학식 3으로 표시되는 옥시인돌 이합체의 제조 방법을 제공한다.Reacting the 3-alkyl-substituted oxyindole with an oxidizing agent and an organic solvent, and refluxing at 50 to 150 ° C in an atmosphere of nitrogen or oxygen; (2) or (3), wherein R < 2 >

Figure 112014001569291-pat00001

Figure 112014001569291-pat00001

(상기 화학식 1 내지 3에서, R1 은 탄소수 1 내지 11의 알킬기, 탄소수 1 내지 11의 알케닐기, 탄소수 1 내지 11의 아릴기, 탄소수 1 내지 11의 헤테로 아릴기, 벤질기, 에스터, 케톤, 알데하이드, 및 에터 중 어느 하나이고,(Wherein R 1 represents an alkyl group having 1 to 11 carbon atoms, an alkenyl group having 1 to 11 carbon atoms, an aryl group having 1 to 11 carbon atoms, a heteroaryl group having 1 to 11 carbon atoms, a benzyl group, an ester, a ketone, Aldehyde, and ether,

R2 는 수소, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 아릴기, 벤질기, 및 할로겐 중 어느 하나임)
R 2 is any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a benzyl group, and halogen)

본 발명은 3-알킬 치환 옥시인돌로서 화학식 1로 표시되는 3-알킬 치환 옥시인돌을 사용하고, 산화제를 첨가함으로써 3-알킬 치환 옥시인돌에 자유 라디칼을 형성시키고, 상기 자유 라디칼이 형성된 3-알킬 치환 옥시인돌이 이합체화 반응(dimerization)을 하여 옥시인돌 이합체를 형성한다.(Free Radical Dimerization) The present invention relates to a process for the production of 3-alkyl-substituted oxyindole by using a 3-alkyl-substituted oxyindole represented by the general formula (1) as a 3-alkyl-substituted oxyindole, Substituted oxyindoles undergo dimerization to form oxyindole dimers (Free Radical Dimerization).

Figure 112014001569291-pat00002

Figure 112014001569291-pat00002

본 발명에 의한 옥시인돌 이합체의 제조 방법에 있어서, 3-알킬 치환 옥시인돌에 자유 라디칼을 형성시킬 수 있는 산화제는 어느 것이라도 사용될 수 있다. 구체적으로 Copper(II) acetate, Silver acetate, Manganese(III) acetate, Ce(NH4)2(NO3)6, FeCl3, K3Fe(CN)6, Palladium(II) acetate, 및 K2S2O8로 이루어진 그룹에서 선택된 산화제를 사용할 수 있다. 특히 Copper(II) acetate 및 Silver acetate의 혼합물 또는 Manganese(III) acetate을 사용하는 경우 보다 고수율로 옥시인돌 이합체를 제조할 수 있다. In the process for producing an oxyindole dimer according to the present invention, any oxidizing agent capable of forming a free radical in a 3-alkyl-substituted oxyindole can be used. Specifically, Copper (II) acetate, Silver acetate , Manganese (III) acetate, Ce (NH 4) 2 (NO 3) 6, FeCl 3, K 3 Fe (CN) 6, Palladium (II) acetate, and K 2 S 2 O < 8 >. In particular, oxyindole dimers can be produced with higher yields than when using a mixture of Copper (II) acetate and Silver acetate or Manganese (III) acetate.

본 발명에 의한 옥시인돌 이합체의 제조 방법에 있어서, 상기 Copper(II) acetate 및 Silver acetate의 혼합물을 산화제로 사용하는 경우, Copper(II) acetate는 출발물질인 3-알킬 치환 옥시인돌 대비 10 내지 30 mol % 포함되고, Silver acetate는 1.0 내지 5.0 당량(equiv.) 혼합될 수 있으며, 바람직하게는 Copper(II) acetate는 15 내지 25 mol % 포함되고, Silver acetate는 2.0 내지 4.5 당량(equiv.) 혼합될 수 있다.In the process for preparing an oxyindole dimer according to the present invention, when a mixture of Copper (II) acetate and Silver acetate is used as an oxidizing agent, Copper (II) acetate is used in an amount of 10 to 30 and silver acetate may be mixed in an amount of 1.0 to 5.0 equivalents, preferably 15 to 25 mol% of Copper (II) acetate and 2.0 to 4.5 equivalent (equiv.) of silver acetate, .

본 발명에 의한 옥시인돌 이합체의 제조 방법에 있어서, 상기 Manganese(III) acetate를 산화제로 사용하는 경우, Manganese(III) acetate는 1.0 내지 5.0 당량(equiv.) 혼합될 수 있으며, 바람직하게는 1.5 내지 2.5 당량(equiv.) 혼합될 수 있다. In the method for producing an oxyindole dimer according to the present invention, when the Manganese (III) acetate is used as an oxidizing agent, Manganese (III) acetate 1.0 to 5.0 equivalents (equiv.), Preferably 1.5 to 2.5 equivalents (equiv.).

본 발명에 의한 옥시인돌 이합체의 제조 방법에 있어서, 상기 유기 용매는 3-알킬 치환 옥시인돌을 용해할 수 있는 용매이면 특별히 제한되지 않으며, 구체적으로 벤젠(benzene), 클로로벤젠, 1,2-디클로로벤젠, 및 이들의 혼합물 등을 용매로 사용할 수 있다. In the process for producing an oxyindole dimer according to the present invention, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving a 3-alkyl-substituted oxyindole, and specifically includes benzene, chlorobenzene, 1,2- Benzene, and mixtures thereof, and the like can be used as a solvent.

본 발명은 질소 또는 산소 분위기에서 환류(reflux) 시키는 단계를 포함하며, 특히 N2 분위기에서 반응을 시키는 경우 아래와 같은 부생성물, 즉 3번 탄소에 산소가 결합된 옥시인돌 화합물이 형성되는 것을 방지할 수 있다.The present invention includes a step of refluxing in an atmosphere of nitrogen or oxygen. In particular, when the reaction is performed in an N 2 atmosphere, the following by-products, that is, the oxyindole compound in which oxygen is bonded to the carbon number 3 is prevented .

Figure 112014001569291-pat00003

Figure 112014001569291-pat00003

본 발명에 있어서, 상기 화학식 1로 표시되는 3-알킬 치환 옥시인돌은 구체적으로 하기 화학식 4일 수 있다. In the present invention, the 3-alkyl-substituted oxyindole represented by the formula (1) may be represented by the following formula (4).

[화학식 4][Chemical Formula 4]

Figure 112014001569291-pat00004
Figure 112014001569291-pat00004

(상기 화학식 4에서, R3 는 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 아릴기, 산소 또는 질소로 치환된 탄소수 1 내지 10의 헤테로 아릴기, 탄소수 1 내지 10의 에스터, 탄소수 1 내지 10의 케톤, 알데하이드, 페닐 비닐기, 페닐 아릴기, 및 탄소수 1 내지 10의 에터기 중 어느 하나이고, (Wherein R 3 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a heteroaryl group having 1 to 10 carbon atoms substituted with oxygen or nitrogen, an ester having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms A ketone, an aldehyde, a phenylvinyl group, a phenylaryl group, and an ether group having 1 to 10 carbon atoms,

R4 는 수소, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 아릴기, 벤질기, 및 할로겐 중 어느 하나임) R 4 is any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a benzyl group, and halogen)

본 발명에 있어서, 상기 화학식 1로 표시되는 3-알킬 치환 옥시인돌은 보다 구체적으로 하기 화학식 5 내지 12 에서 선택된 어느 하나일 수 있다.In the present invention, the 3-alkyl-substituted oxyindole represented by the formula (1) may be any one selected from the following formulas (5) to (12).

Figure 112014001569291-pat00005

Figure 112014001569291-pat00005

또한 본 발명은, 본 발명의 제조 방법에 의하여 제조된 옥시인돌 이합체를 제공하며, 상기 옥시인돌 이합체는 아래 화학식 13 내지 20의 D-form, L-form, 및 메조(meso) 화합물 중 어느 하나일 수 있다.The present invention also provides an oxyindole duplex produced by the production method of the present invention, wherein the oxyindole duplex is any one of D-form , L-form , and meso compounds of the following formulas (13) to .

Figure 112014001569291-pat00006

Figure 112014001569291-pat00006

본 발명에 의한 옥시인돌 이합체의 제조 방법은 3-알킬 치환 옥시인돌 및 산화제를 혼합한 후 환류(reflux) 반응을 통해 옥시인돌 이합체를 제조함으로써, 직접적으로 3-알킬 치환 옥시인돌의 3번 탄소 간에 단일 결합을 형성시켜 옥시인돌 이합체를 고수율로 제조할 수 있다.
The process for producing an oxyindole dimer according to the present invention is characterized in that an oxyindole dimer is prepared by mixing a 3-alkyl-substituted oxyindole and an oxidizing agent and then refluxing the mixture, A single bond can be formed to produce an oxyindole duplex at a high yield.

이하에서는 본 발명을 실시예에 의하여 더욱 상세히 설명한다. 그러나, 본 발명이 이하의 실시예에 의하여 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples.

<< 실시예Example 1> 3,3'- 1 > 3,3'- dibenzyldibenzyl -1,1'--1,1'- dimethyldimethyl -1,3,1',3'--1,3,1 ', 3'- tetrahydrotetrahydro -[3,3']biindolyl-2,2'-dione 의 제조- [3,3 '] biindolyl-2,2'-dione

반응물로서 3-알킬 치환 옥시인돌인 3-benzyl-1-methyl-1,3-dihydro-indol-2-one로부터 아래 반응식과 같이 3,3'-dibenzyl-1,1'-dimethyl-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 을 제조하였다.3,3'-dibenzyl-1,1'-dimethyl-1,3-dihydroindol-2-one was prepared from 3-alkyl substituted oxyindole, 3-benzyl-1-methyl- , 1 ', 3'-tetrahydro- [3,3'] biindolyl-2,2'-dione.

Figure 112014001569291-pat00007

Figure 112014001569291-pat00007

반응물 3-benzyl-1-methyl-1,3-dihydro-indol-2-one을 0.5 mmol(119 mg) 사용하고, 산화제의 종류 및 양을 아래 표 1과 같이 달리하여 2 ml 벤젠 용매에 혼합하고 N2 또는 O2 분위기에서 환류(reflux) 시켰다. 0.5 mmol (119 mg) of the reactant 3-benzyl-1-methyl-1,3-dihydro-indol-2-one was used and the kind and amount of the oxidizing agent were changed as shown in Table 1 below and mixed in a 2 ml benzene solvent Was refluxed in an N 2 or O 2 atmosphere.

EntryEntry ConditionsConditions 1One Cu(OAc)2 (20 mol %), AgOAc (4.5 equiv), benzeneCu (OAc) 2 (20 mol%), AgOAc (4.5 equiv), benzene O2, reflux, 4 hO 2 , reflux, 4 h 22 AgOAc (4.5 equiv), benzeneAgOAc (4.5 equiv), benzene O2, reflux, 12 hO 2 , reflux, 12 h 33 Cu(OAc)2 (20 mol %), benzeneCu (OAc) 2 (20 mol%), benzene O2, reflux, 36 hO 2 , reflux, 36 h 44 Cu(OAc)2 (2.2 equiv), benzeneCu (OAc) 2 (2.2 equiv), benzene O2 reflux, 72 hO 2 reflux, 72 h 55 Cu(OAc)2 (20 mol %), AgOAc (2.0 equiv), benzeneCu (OAc) 2 (20 mol%), AgOAc (2.0 equiv), benzene O2, reflux, 24 hO 2 , reflux, 24 h 66 Cu(OAc)2 (20 mol %), AgOAc (2.0 equiv), benzeneCu (OAc) 2 (20 mol%), AgOAc (2.0 equiv), benzene N2, reflux, 36 hN 2 , reflux, 36 h 77 Cu(OAc)2 (20 mol %), K2S2O8 (2.0 equiv), benzeneCu (OAc) 2 (20 mol%), K 2 S 2 O 8 (2.0 equiv), benzene N2, reflux, 48 hN 2 , reflux, 48 h 88 Mn(OAc)3 (2.0 equiv), benzeneMn (OAc) 3 (2.0 equiv), benzene N2, reflux, 4 hN 2 , reflux, 4 h 99 Mn(OAc)3 (1.1 equiv), benzeneMn (OAc) 3 (1.1 equiv), benzene N2, reflux, 12 hN 2 , reflux, 12 h 1010 Ce(NH4)2(NO3)6 (2.0 equiv), benzene Ce (NH 4) 2 (NO 3) 6 (2.0 equiv), benzene N2, reflux, 4 hN 2 , reflux, 4 h 1111 FeCl3 (2.0 equiv), benzeneFeCl 3 (2.0 equiv), benzene N2, reflux, 15 hN 2 , reflux, 15 h 1212 K3Fe(CN)6 (2.0 equiv), benzeneK 3 Fe (CN) 6 (2.0 equiv), benzene N2, reflux, 36 hN 2 , reflux, 36 h

이어서 증류수로 생성물을 추출하고, hexanes/CH2Cl2/ether가 10:3:1 의 부피비로 혼합된 용매로 컬럼 크로마토그래피를 수행하여 생성물을 다음과 같이 정제하였다.
The product was then extracted with distilled water and column chromatographed with a solvent mixture hexanes / CH 2 Cl 2 / ether in a volume ratio of 10: 3: 1 to purify the product as follows.

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.51 (hexanes/ether, 1:3); pale yellow solid, mp 211-212 ℃; R f = 0.51 (hexanes / ether , 1: 3); pale yellow solid, mp 211-212 [deg.] C;

IR (KBr) 1703, 1611, 1471, 1376 cm-1;IR (KBr) 1703, 1611, 1471, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz): δ 2.82 (s, 6H), 3.70 (d, J = 12.6 Hz, 2H), 4.24 (d, J = 12.6 Hz, 2H), 6.07 (d, J = 7.5 Hz, 2H), 6.68 (t, J = 7.5 Hz, 2H), 6.72-6.92 (m, 12H), 7.12 (d, J = 7.5 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz): δ 2.82 (s, 6H), 3.70 (d, J = 12.6 Hz, 2H), 4.24 (d, J = 12.6 Hz, 2H), 6.07 (d, J = 7.5 Hz, 2H), 6.68 (t, J = 7.5 Hz, 2H), 6.72-6.92 (m, 12H), 7.12 (d, J = 7.5 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 25.42, 35.28, 57.43, 107.10, 121.40, 123.86, 125.98, 127.23, 127.93, 128.17, 130.30, 135.97, 142.99, 176.94; 13 C NMR (CDCl 3 , 75 MHz) δ 25.42, 35.28, 57.43, 107.10, 121.40, 123.86, 125.98, 127.23, 127.93, 128.17, 130.30, 135.97, 142.99, 176.94;

ESIMS m/z 473 [M+H]+.ESIMS m / z 473 [M + H] &lt; + &gt;.

Anal. Calcd for C32H28N2O2: C, 81.33; H, 5.97; N, 5.93.Anal. Calcd for C32H28N2O2: C, 81.33; H, 5.97; N, 5.93.

Found: C, 81.14; H, 6.07; N, 5.78.
Found: C, 81.14; H, 6.07; N, 5.78.

(2)(2) mesomeso compoundcompound

R f = 0.23 (hexanes/ether, 1:3); pale yellow solid, mp 221-222 ℃; R f = 0.23 (hexanes / ether , 1: 3); pale yellow solid, mp 221-222 [deg.] C;

IR (KBr) 1703, 1609, 1471, 1375 cm-1;IR (KBr) 1703, 1609, 1471, 1375 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 2.60 (s, 6H), 3.42 (d, J = 12.6 Hz, 2H), 4.18 (d, J = 12.6 Hz, 2H), 6.34 (d, J = 7.8 Hz, 2H), 6.66-6.96 (m, 14H), 7.07 (t, J = 7.8 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 2.60 (s, 6H), 3.42 (d, J = 12.6 Hz, 2H), 4.18 (d, J = 12.6 Hz, 2H), 6.34 (d, J = 7.8 Hz , 2H), 6.66-6.96 (m, 14H), 7.07 (t, J = 7.8 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 25.51, 36.82, 58.08, 107.72, 121.26, 124.56, 126.17, 127.20, 128.46, 128.51, 130.32, 135.35, 144.37, 175.88; 13 C NMR (CDCl 3 , 75 MHz) δ 25.51, 36.82, 58.08, 107.72, 121.26, 124.56, 126.17, 127.20, 128.46, 128.51, 130.32, 135.35, 144.37, 175.88;

ESIMS m/z 473 [M+H]+. ESIMS m / z 473 [M + H] &lt; + &gt;.

Anal. Calcd for C32H28N2O2: C, 81.33; H, 5.97; N, 5.93. Anal. Calcd for C32H28N2O2: C, 81.33; H, 5.97; N, 5.93.

Found: C, 81.41; H, 6.02; N, 5.66.
Found: C, 81.41; H, 6.02; N, 5.66.

<< 실험예Experimental Example > 반응조건에 따른 수율 측정> Measurement of yield by reaction conditions

상기 실시예 1에서 제조된 옥시인돌 이합체의 수율을 측정하고 아래 표 2에 나타내었다. The yield of the oxyindole duplex prepared in Example 1 was measured and shown in Table 2 below.

EntryEntry 옥시인돌 이합체의 수율Yield of oxyindole dimer dl (%)/meso (%)dl (%) / meso (%) 반응물(%)Reactant (%) 1One 7878 40 / 3840/38 00 22 00 0 / 00/0 9898 33 < 10<10 < 5 / < 5<5 / <5 8585 44 6363 32 / 3132/31 2626 55 8282 43 / 3943/39 00 66 8888 46 / 4246/42 00 77 7171 36 / 3536/35 99 88 9090 46 / 4446/44 00 99 8282 42 / 4042/40 66 1010 1919 10 / 910/9 99 1111 1717 9 / 89/8 6060 1212 6666 32 / 3432/34 1414

상기 표 2에서 dl (%)/meso (%) 는 정제 수율(isolated yield)을 의미한다. 상기 표 2에서 보는 바와 같이 entry 6과 8의 경우 가장 좋은 수율을 나타냄을 알 수 있다. 이하에서는 entry 6을 Condition A로 하고, entry 8을 Condition B로 한다.
In Table 2, dl (%) / meso (%) means an isolated yield. As shown in Table 2, it can be seen that entry 6 and 8 show the best yields. Hereinafter, entry 6 is defined as Condition A, and entry 8 is defined as Condition B.

<< 실시예Example 2> 다양한 3- 2> Various 3- 알킬Alkyl 치환  substitution 옥시인돌로부터From oxyindole 옥시인돌Oxyindole 이합체의Dimer 제조  Produce

<< 실시예Example 2-1> 3,3'- 2-1> 3,3'- diethyldiethyl -1,1'--1,1'- dimethyldimethyl -1,3,1',3'--1,3,1 ', 3'- tetrahydrotetrahydro -[3,3'] biindolyl-2,2'-dione 의 제조- [3,3 '] biindolyl-2,2'-dione

하기 반응식에 따라 Condition B의 조건에서 실시예 1과 동일하게 하여 3,3'-diethyl-1,1'-dimethyl-1,3,1',3'-tetrahydro-[3,3'] biindolyl-2,2'-dione 을 합성하였다. D-form 및 L-form 은 46 %, 메조화합물은 43 %의 수율을 나타냈다. According to the following reaction scheme, 3,3'-diethyl-1,1'-dimethyl-1,3,1 ', 3'-tetrahydro- [3,3'] biindolyl- 2,2'-dione was synthesized. The yields of D-form and L-form were 46% and meso compound was 43%.

Figure 112014001569291-pat00008
Figure 112014001569291-pat00008

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.43 (hexanes/ether, 1:3); white solid, mp 231-232 ℃; R f = 0.43 (hexanes / ether, 1: 3); white solid, mp 231-232 [deg.] C;

IR (KBr) 1704, 1609, 1493, 1355 cm-1; IR (KBr) 1704, 1609, 1493, 1355 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.33 (t, J = 7.5 Hz, 6H), 2.20-2.36 (m, 2H), 2.62-2.80 (m, 2H), 3.00 (s, 6H), 6.34 (d, J = 7.5 Hz, 2H), 6.75 (t, J = 7.5 Hz, 2H), 6.88-7.00 (m, 4H); 1 H NMR (CDCl 3, 300 MHz) δ 0.33 (t, J = 7.5 Hz, 6H), 2.20-2.36 (m, 2H), 2.62-2.80 (m, 2H), 3.00 (s, 6H), 6.34 ( d, J = 7.5 Hz, 2H), 6.75 (t, J = 7.5 Hz, 2H), 6.88-7.00 (m, 4H);

13C NMR (CDCl3, 75 MHz) δ 8.86, 21.42, 25.52, 57.39, 107.10, 121.55, 123.03, 127.90, 128.65, 143.52, 177.50; 13 C NMR (CDCl 3 , 75 MHz) δ 8.86, 21.42, 25.52, 57.39, 107.10, 121.55, 123.03, 127.90, 128.65, 143.52, 177.50;

ESIMS m/z 349 [M+H]+. ESIMS m / z 349 [M + H] &lt; + &gt;.

Anal. Calcd for C22H24N2O2: C, 75.83; H, 6.94; N, 8.04. Anal. Calcd for C22H24N2O2: C, 75.83; H, 6.94; N, 8.04.

Found: C, 75.91; H, 7.10; N, 7.89.
Found: C, 75.91; H, 7.10; N, 7.89.

(2)(2) mesomeso compoundcompound

R f = 0.14 (hexanes/ether, 1:3); white solid, mp 201-202 ℃; IR (KBr) 1711, 1609, 1468, 1350 cm-1; R f = 0.14 (hexanes / ether , 1: 3); white solid, mp 201-202 [deg.] C; IR (KBr) 1711, 1609, 1468, 1350 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.36 (t, J = 7.5 Hz, 6H), 1.94-2.12 (m, 2H), 2.60-2.78 (m, 2H), 2.88 (s, 6H), 6.47 (d, J = 7.8 Hz, 2H), 6.62 (d, J = 7.8 Hz, 2H), 6.78 (t, J = 7.8 Hz, 2H), 7.16 (t, J = 7.8 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 0.36 (t, J = 7.5 Hz, 6H), 1.94-2.12 (m, 2H), 2.60-2.78 (m, 2H), 2.88 (s, 6H), 6.47 ( d, J = 7.8 Hz, 2H), 6.62 (d, J = 7.8 Hz, 2H), 6.78 (t, J = 7.8 Hz, 2H), 7.16 (t, J = 7.8 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 8.57, 22.94, 25.70, 57.85, 107.55, 121.37, 123.80, 128.31, 128.77, 144.79, 176.69; 13 C NMR (CDCl 3, 75 MHz) δ 8.57, 22.94, 25.70, 57.85, 107.55, 121.37, 123.80, 128.31, 128.77, 144.79, 176.69;

ESIMS m/z 349 [M+H]+.
ESIMS m / z 349 [M + H] &lt; + &gt;.

<< 실시예Example 2-2> 3'- 2-2 > 3'- EthoxycarbonylmethylEthoxycarbonylmethyl -1,1'--1,1'- dimethyldimethyl -2,2'--2,2'- dioxodioxo -1,2,2',3'-tetrahydro-1'H-[3,3']biindolyl-3-yl)-acetic -1,2,2 ', 3'-tetrahydro-1'H- [3,3'] biindolyl-3-yl) -acetic acidacid ethylethyl ester 의ester 제조 Produce

하기 반응식에 따라 상기 Condition A의 조건에서 실시예 1과 동일하게 하여 3'-Ethoxycarbonylmethyl-1,1'-dimethyl-2,2'-dioxo-1,2,2',3'-tetrahydro-1'H-[3,3']biindolyl-3-yl)-acetic acid ethyl ester 을 합성하였다. D-form 및 L-form 은 45 %, 메조화합물은 41 %의 수율을 나타냈다. 1,1'-dimethyl-2,2'-dioxo-1,2,2 ', 3'-tetrahydro-1', 4'-tetrahydro- H- [3,3 '] biindolyl-3-yl) -acetic acid ethyl ester. 45% for D-form and L-form, and 41% for meso compound.

Figure 112014001569291-pat00009
Figure 112014001569291-pat00009

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.50 (hexanes/ether, 1:4); pale yellow solid, mp 191-192 ℃; R f = 0.50 (hexanes / ether , 1: 4); pale yellow solid, mp 191-192 DEG C;

IR (KBr) 1737, 1711, 1612, 1471, 1376 cm-1;IR (KBr) 1737, 1711, 1612, 1471, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.83 (t, J = 6.9 Hz, 6H), 3.02 (s, 6H), 3.12 (d, J = 15.9 Hz, 2H), 3.60-3.82 (m, 4H), 3.96 (d, J = 15.9 Hz, 2H), 6.32 (d, J = 7.8 Hz, 2H), 6.74 (t, J = 7.8 Hz, 2H), 6.95 (t, J = 7.8 Hz, 2H), 6.96 (d, J = 7.8 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 0.83 (t, J = 6.9 Hz, 6H), 3.02 (s, 6H), 3.12 (d, J = 15.9 Hz, 2H), 3.60-3.82 (m, 4H) , 3.96 (d, J = 15.9 Hz, 2H), 6.32 (d, J = 7.8 Hz, 2H), 6.74 (d, J = 7.8 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 13.72, 25.74, 33.92, 52.42, 60.33, 107.24, 121.37, 122.81, 126.82, 128.74, 143.83, 169.72, 176.57; 13 C NMR (CDCl 3 , 75 MHz) 隆 13.72, 25.74, 33.92, 52.42, 60.33, 107.24, 121.37, 122.81, 126.82, 128.74, 143.83, 169.72, 176.57;

ESIMS m/z 465 [M+H]+.
ESIMS m / z 465 [M + H] &lt; + &gt;.

(2)(2) mesomeso compoundcompound

R f = 0.23 (hexanes/ether, 1:4); pale yellow solid, mp 153-154 ℃; R f = 0.23 (hexanes / ether , 1: 4); pale yellow solid, mp 153-154 [deg.] C;

IR (KBr) 1737, 1718, 1611, 1471, 1376 cm-1; IR (KBr) 1737, 1718, 1611, 1471, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.85 (t, J = 7.2 Hz, 6H), 2.89 (s, 6H), 3.06 (d, J = 16.2 Hz, 2H), 3.68 (d, J = 16.2 Hz, 2H), 3.60-3.84 (m, 4H), 6.46 (d, J = 7.5 Hz, 2H), 6.63 (d, J = 7.5 Hz, 2H), 6.77 (t, J = 7.5 Hz, 2H), 7.19 (t, J = 7.5 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 0.85 (t, J = 7.2 Hz, 6H), 2.89 (s, 6H), 3.06 (d, J = 16.2 Hz, 2H), 3.68 (d, J = 16.2 Hz (D, J = 7.5 Hz, 2H), 3.60-3.84 (m, 4H), 6.46 (t, J = 7.5 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 13.72, 25.99, 35.58, 53.13, 60.49, 107.88, 121.35, 123.44, 127.11, 129.15, 145.08, 169.30, 175.50; 13 C NMR (CDCl 3 , 75 MHz) 隆 13.72, 25.99, 35.58, 53.13, 60.49, 107.88, 121.35, 123.44, 127.11, 129.15, 145.08, 169.30, 175.50;

ESIMS m/z 465 [M+H]+.ESIMS m / z 465 [M + H] &lt; + &gt;.

Anal. Calcd for C26H28N2O6: C, 67.23; H, 6.08; N, 6.03. Anal. Calcd for C26H28N2O6: C, 67.23; H, 6.08; N, 6.03.

Found: C, 67.52; H, 6.34; N, 5.82.
Found: C, 67.52; H, 6.34; N, 5.82.

<< 실시예Example 2-3> 1,1'- 2-3> 1,1'- DimethylDimethyl -3,3'--3,3'- bisbis -(2--(2- oxooxo -2--2- phenylphenyl -- ethylethyl )-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 의 제조) -1,3,1 ', 3'-tetrahydro- [3,3'] biindolyl-2,2'-dione

하기 반응식에 따라 Condition B의 조건에서 실시예 1과 동일하게 하여 1,1'-Dimethyl-3,3'-bis-(2-oxo-2-phenyl-ethyl)-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 을 합성하였다. D-form 및 L-form 은 43 %, 메조화합물은 40 %의 수율을 나타냈다. According to the following reaction scheme, 1,1'-Dimethyl-3,3'-bis- (2-oxo-2-phenyl-ethyl) -1,3,1 ', 3 -tetrahydro- [3,3 '] biindolyl-2,2'-dione. 43% for D-form and L-form, and 40% for meso compound.

Figure 112014001569291-pat00010
Figure 112014001569291-pat00010

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.43 (hexanes/ether, 1:4); pale yellow solid, mp 233-234 ℃; R f = 0.43 (hexanes / ether , 1: 4); pale yellow solid, mp 233-234 [deg.] C;

IR (KBr) 1703, 1612, 1471, 1344 cm-1;IR (KBr) 1703, 1612, 1471, 1344 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 3.11 (s, 6H), 3.75 (d, J = 17.7 Hz, 2H), 5.03 (d, J = 17.7 Hz, 2H), 6.35 (d, J = 7.2 Hz, 2H), 6.65 (t, J = 7.2 Hz, 2H), 6.85 (d, J = 7.2 Hz, 2H), 6.92 (t, J = 7.2 Hz, 2H), 7.28-7.52 (m, 6H), 7.84 (d, J = 7.2 Hz, 4H); 1 H NMR (CDCl 3, 300 MHz) δ 3.11 (s, 6H), 3.75 (d, J = 17.7 Hz, 2H), 5.03 (d, J = 17.7 Hz, 2H), 6.35 (d, J = 7.2 Hz J = 7.2 Hz, 2 H), 6.85 (d, J = 7.2 Hz, 2H), 6.65 (d, J = 7.2 Hz, 4H);

13C NMR (CDCl3, 150 MHz) δ 25.89, 38.16, 52.69, 107.29, 121.17, 121.97, 127.35, 128.15, 128.47, 128.48, 133.26, 136.42, 144.03, 177.49, 196.45; 13 C NMR (CDCl 3 , 150 MHz) δ 25.89, 38.16, 52.69, 107.29, 121.17, 121.97, 127.35, 128.15, 128.47, 128.48, 133.26, 136.42, 144.03, 177.49, 196.45;

ESIMS m/z 529 [M+H]+.
ESIMS m / z 529 [M + H] &lt; + &gt;.

(2)(2) mesomeso compoundcompound

R f = 0.16 (hexanes/ether, 1:4); pale yellow solid, mp 203-204 ℃; R f = 0.16 (hexanes / ether , 1: 4); pale yellow solid, mp 203-204 [deg.] C;

IR (KBr) 1712, 1612, 1470, 1347 cm-1;IR (KBr) 1712, 1612, 1470, 1347 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 2.94 (s, 6H), 3.95 (d, J = 17.4 Hz, 2H), 4.52 (d, J = 17.4 Hz, 2H), 6.41 (br s, 2H), 6.69 (d, J = 7.8 Hz, 2H), 6.74 (t, J = 7.8 Hz, 2H), 7.19 (t, J = 7.8 Hz, 2H), 7.33 (t, J = 7.2 Hz, 4H), 7.46 (t, J = 7.2 Hz, 2H), 7.79 (d, J = 7.2 Hz, 4H); 1 H NMR (CDCl 3, 300 MHz) δ 2.94 (s, 6H), 3.95 (d, J = 17.4 Hz, 2H), 4.52 (d, J = 17.4 Hz, 2H), 6.41 (br s, 2H), J = 7.8 Hz, 2H), 6.74 (t, J = 7.8 Hz, 2H), 7.19 (t, t, J = 7.2 Hz, 2H), 7.79 (d, J = 7.2 Hz, 4H);

13C NMR (CDCl3, 150 MHz) δ 26.10, 39.94, 53.32, 108.05, 121.07, 122.65, 127.95, 127.97, 128.47, 128.90, 133.21, 136.43, 145.40, 176.06, 195.48; 13 C NMR (CDCl 3 , 150 MHz)? 26.10, 39.94, 53.32, 108.05, 121.07, 122.65, 127.95, 127.97, 128.47, 128.90, 133.21, 136.43, 145.40, 176.06, 195.48;

ESIMS m/z 529 [M+H]+.ESIMS m / z 529 [M + H] &lt; + &gt;.

Anal. Calcd for C34H28N2O4: C, 77.25; H, 5.34; N, 5.30. Anal. Calcd for C34H28N2O4: C, 77.25; H, 5.34; N, 5.30.

Found: C, 77.29; H, 5.53; N, 5.24.
Found: C, 77.29; H, 5.53; N, 5.24.

<< 실시예Example 2-4> (1,1'- 2-4> (1,1'- DibenzylDibenzyl -3'--3'- ethoxycarbonylmethylethoxycarbonylmethyl -2,2'--2,2'- dioxodioxo -1,2,2',3'-tetrahydro-1'H-[3,3']biindolyl-3-yl)-acetic -1,2,2 ', 3'-tetrahydro-1'H- [3,3'] biindolyl-3-yl) -acetic acidacid ethylethyl ester 의ester 제조 Produce

하기 반응식에 따라 Condition B의 조건에서 실시예 1과 동일하게 하여 (1,1'-Dibenzyl-3'-ethoxycarbonylmethyl-2,2'-dioxo-1,2,2',3'-tetrahydro-1'H-[3,3']biindolyl-3-yl)-acetic acid ethyl ester 을 합성하였다. D-form 및 L-form 은 40 %, 메조화합물은 38 %의 수율을 나타냈다. According to the following reaction scheme, (1,1'-Dibenzyl-3'-ethoxycarbonylmethyl-2,2'-dioxo-1,2,2 ', 3'-tetrahydro- H- [3,3 '] biindolyl-3-yl) -acetic acid ethyl ester. The yields of D-form and L-form were 40% and meso compound was 38%.

Figure 112014001569291-pat00011
Figure 112014001569291-pat00011

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.63 (hexanes/ether, 1:3); white solid, mp 150-152 ℃; R f = 0.63 (hexanes / ether , 1: 3); white solid, mp 150-152 [deg.] C;

IR (KBr) 1736, 1709, 1612, 1467, 1368 cm-1;IR (KBr) 1736, 1709, 1612, 1467, 1368 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.74 (t, J = 7.2 Hz, 6H), 3.19 (d, J = 15.9 Hz, 2H), 3.54-3.84 (m, 4H), 4.05 (d, J = 15.9 Hz, 2H), 4.45 (d, J = 15.6 Hz, 2H), 4.99 (d, J = 15.6 Hz, 2H), 6.26 (d, J = 7.8 Hz, 2H), 6.57 (t, J = 7.8 Hz, 2H), 6.84 (t, J =7.8 Hz, 2H), 6.94 (d, J = 7.8 Hz, 2H), 7.14-7.30 (m, 10H); 1 H NMR (CDCl 3, 300 MHz) δ 0.74 (t, J = 7.2 Hz, 6H), 3.19 (d, J = 15.9 Hz, 2H), 3.54-3.84 (m, 4H), 4.05 (d, J = J = 7.8 Hz, 2H), 4.45 (d, J = 15.6 Hz, 2H), 4.99 (d, J = , 6.84 (t, J = 7.8 Hz, 2H), 6.94 (d, J = 7.8 Hz, 2H), 7.14-7.30 (m, 10H);

13C NMR (CDCl3, 150 MHz) δ 13.66, 34.50, 44.31, 52.33, 60.40, 108.45, 121.68, 123.55, 126.76, 127.47, 127.81, 128.55, 128.57, 135.42, 143.41, 169.61, 176.90; 13 C NMR (CDCl 3 , 150 MHz)? 13.66, 34.50, 44.31, 52.33, 60.40, 108.45, 121.68, 123.55, 126.76, 127.47, 127.81, 128.55, 128.57, 135.42, 143.41, 169.61, 176.90;

ESIMS m/z 617 [M+H]+.ESIMS m / z 617 [M + H] &lt; + &gt;.

Anal. Calcd for C38H36N2O6: C, 74.01; H, 5.88; N, 4.54. Anal. Calcd for C38H36N2O6: C, 74.01; H, 5.88; N, 4.54.

Found: C, 74.35; H, 5.93; N, 4.48.
Found: C, 74.35; H, 5.93; N, 4.48.

(2)(2) mesomeso compoundcompound

R f = 0.49 (hexanes/ether, 1:3); white solid, mp 84-86 ℃; R f = 0.49 (hexanes / ether , 1: 3); white solid, mp 84-86 [deg.] C;

IR (KBr) 1735, 1721, 1610, 1467, 1367 cm-1;IR (KBr) 1735, 1721, 1610, 1467, 1367 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.81 (t, J = 7.2 Hz, 6H), 3.17 (d, J = 15.9 Hz, 2H), 3.72 (d, J = 15.9 Hz, 2H), 3.55-3.60 (m, 4H), 4.54 (d, J = 15.9 Hz, 2H), 4.85 (d, J = 15.9 Hz, 2H), 6.46 (d, J = 7.5 Hz, 2H), 6.73 (br s, 2H), 6.86-7.26 (m, 14H); 1 H NMR (CDCl 3, 300 MHz) δ 0.81 (t, J = 7.2 Hz, 6H), 3.17 (d, J = 15.9 Hz, 2H), 3.72 (d, J = 15.9 Hz, 2H), 3.55-3.60 (m, 4H), 4.54 (d, J = 15.9 Hz, 2H), 4.85 (d, J = 15.9 Hz, 2H), 6.46 6.86-7.26 (m, 14H);

13C NMR (CDCl3, 150 MHz) δ 13.75, 36.46, 44.58, 52.94, 60.60, 109.33, 121.73, 123.72, 127.11, 127.25, 128.48 (2C), 129.14, 135.71, 144.73, 169.23, 176.08; 13 C NMR (CDCl 3 , 150 MHz)? 13.75, 36.46, 44.58, 52.94, 60.60, 109.33, 121.73, 123.72, 127.11, 127.25, 128.48 (2C), 129.14, 135.71, 144.73, 169.23, 176.08;

ESIMS m/z 617 [M+H]+.
ESIMS m / z 617 [M + H] &lt; + &gt;.

<< 실시예Example 2-5> (3'- 2-5> (3'- EthoxycarbonylmethylEthoxycarbonylmethyl -2,2'--2,2'- dioxodioxo -1,2,2',3'--1, 2, 2 ', 3'- tetrahydrotetrahydro -1'H-[3,3']biindolyl-3-yl)-acetic -1 ' H- [3,3 '] biindolyl-3-yl) -acetic acidacid ethylethyl ester 의ester 제조 Produce

하기 반응식에 따라 Condition A 또는 B의 조건에서 실시예 1과 동일하게 하여 (3'-Ethoxycarbonylmethyl-2,2'-dioxo-1,2,2',3'-tetrahydro-1'H-[3,3']biindolyl-3-yl)-acetic acid ethyl ester 을 합성하였다. Condition A의 경우 D-form 및 L-form 은 30 %, 메조화합물은 28 %의 수율을 나타냈으며, Condition B의 경우 D-form 및 L-form 은 29 %, 메조화합물은 29 %의 수율을 나타냈다.According to the following reaction scheme, (3'-Ethoxycarbonylmethyl-2,2'-dioxo-1,2,2 ', 3'-tetrahydro-1'H- [3, 3 '] biindolyl-3-yl) -acetic acid ethyl ester. In Condition A, the yields of D-form and L-form were 30% and that of meso compound was 28%. In Condition B, the yields of D-form and L-form were 29% and meso compound was 29% .

Figure 112014001569291-pat00012
Figure 112014001569291-pat00012

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.44 (CH2Cl2/MeOH, 19:1); white solid, mp 241-242 ℃; R f = 0.44 (CH 2 Cl 2 / MeOH, 19: 1); white solid, mp 241-242 [deg.] C;

IR (KBr) 3283, 1732, 1620, 1473, 1373 cm-1; IR (KBr) 3283, 1732, 1620, 1473, 1373 cm &lt; -1 & gt ;;

1H NMR (CDCl3+DMSO-d6, 300 MHz) δ 0.91 (t, J = 7.5 Hz, 6H), 3.13 (d, J = 15.6 Hz, 2H), 3.65-3.90 (m, 4H), 4.03 (d, J = 15.6 Hz, 2H), 6.48 (d, J = 7.5 Hz, 2H), 6.79 (t, J = 7.5 Hz, 2H), 6.95 (t, J = 7.5 Hz, 2H), 7.22 (d, J = 7.5 Hz, 2H), 9.14 (s, 2H); 1 H NMR (CDCl 3 + DMSO -d 6, 300 MHz) δ 0.91 (t, J = 7.5 Hz, 6H), 3.13 (d, J = 15.6 Hz, 2H), 3.65-3.90 (m, 4H), 4.03 (t, J = 7.5 Hz, 2H), 6.48 (d, J = 7.5 Hz, 2H), 6.79 , &Lt; / RTI &gt; J = 7.5 Hz, 2H), 9.14 (s, 2H);

13C NMR (CDCl3+DMSO-d6, 150 MHz) δ 13.51, 34.05, 52.49, 60.17, 108.82, 121.16, 123.66, 127.02, 128.38, 141.45, 169.66, 178.31; 13 C NMR (CDCl 3 + DMSO-d 6 , 150 MHz)? 13.51, 34.05, 52.49, 60.17, 108.82, 121.16, 123.66, 127.02, 128.38, 141.45, 169.66, 178.31;

ESIMS m/z 437 [M+H]+.ESIMS m / z 437 [M + H] &lt; + &gt;.

Anal. Calcd for C24H24N2O6: C, 66.04; H, 5.54; N, 6.42.Anal. Calcd for C24H24N2O6: C, 66.04; H, 5.54; N, 6.42.

Found: C, 66.37; H, 5.41; N, 6.38.
Found: C, 66.37; H, 5.41; N, 6.38.

(2)(2) mesomeso compoundcompound

R f = 0.34 (CH2Cl2/MeOH, 19:1); white solid, mp 169-170 ℃; R f = 0.34 (CH 2 Cl 2 / MeOH, 19: 1); white solid, mp 169-170 [deg.] C;

IR (KBr) 3276, 1730, 1620, 1473, 1372 cm-1; IR (KBr) 3276, 1730, 1620, 1473, 1372 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 0.89 (t, J = 6.9 Hz, 6H), 3.08 (d, J = 16.2 Hz, 2H), 3.67 (d, J = 16.2 Hz, 2H), 3.60-4.00 (m, 4H), 6.50 (br s, 2H), 6.68 (d, J = 7.8 Hz, 2H), 6.78 (t, J = 7.8 Hz, 2H), 7.13 (t, J = 7.8 Hz, 2H), 7.67 (s, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 0.89 (t, J = 6.9 Hz, 6H), 3.08 (d, J = 16.2 Hz, 2H), 3.67 (d, J = 16.2 Hz, 2H), 3.60-4.00 (m, 4H), 6.50 (br s, 2H), 6.68 (d, J = 7.8 Hz, 2H), 6.78 (t, J = 7.8 Hz, 2H) 7.67 (s, 2H);

13C NMR (CDCl3, 75 MHz) δ 13.67, 35.87, 53.50, 60.72, 109.96, 121.56, 124.02, 127.61, 129.22, 142.37, 169.43, 177.24; 13 C NMR (CDCl 3 , 75 MHz) 隆 13.67, 35.87, 53.50, 60.72, 109.96, 121.56, 124.02, 127.61, 129.22, 142.37, 169.43, 177.24;

ESIMS m/z 437 [M+H]+.ESIMS m / z 437 [M + H] &lt; + &gt;.

Anal. Calcd for C24H24N2O6: C, 66.04; H, 5.54; N, 6.42. Anal. Calcd for C24H24N2O6: C, 66.04; H, 5.54; N, 6.42.

Found: C, 66.20; H, 5.72; N, 6.24.
Found: C, 66.20; H, 5.72; N, 6.24.

<< 실시예Example 2-6> 3,3'- 2-6 > 3,3'- BisBis -- furanfuran -2--2- ylmethylylmethyl -1,1'--1,1'- dimethyldimethyl -1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 의 제조-1,3,1 ', 3'-tetrahydro- [3,3'] biindolyl-2,2'-dione

하기 반응식에 따라 Condition B의 조건에서 실시예 1과 동일하게 하여 3,3'-Bis-furan-2-ylmethyl-1,1'-dimethyl-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 을 합성하였다. D-form 및 L-form 은 27 %, 메조화합물은 24 %의 수율을 나타냈다. Furan-2-ylmethyl-1,1'-dimethyl-1,3,1 ', 3'-tetrahydro-3,3'-triphosphate was prepared in the same manner as in Example 1, , 3 '] biindolyl-2,2'-dione. 27% for D-form and L-form, and 24% for meso compound.

Figure 112014001569291-pat00013
Figure 112014001569291-pat00013

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.57 (hexanes/ether, 1:3); white solid, mp 253-254 ℃; R f = 0.57 (hexanes / ether , 1: 3); white solid, mp 253-254 [deg.] C;

IR (KBr) 1713, 1611, 1470, 1376 cm-1; IR (KBr) 1713, 1611, 1470, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 2.95 (s, 6H), 3.63 (d, J = 14.4 Hz, 2H), 4.34 (d, J = 14.4 Hz, 2H), 5.56 (d, J = 2.7 Hz, 2H), 5.86 (app s, 2H), 6.21 (d, J = 7.5 Hz, 2H), 6.70 (t, J = 7.5 Hz, 2H), 6.85 (t, J = 7.5 Hz, 2H), 6.88 (s, 2H), 7.04 (d, J = 7.5 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 2.95 (s, 6H), 3.63 (d, J = 14.4 Hz, 2H), 4.34 (d, J = 14.4 Hz, 2H), 5.56 (d, J = 2.7 Hz J = 7.5 Hz, 2H), 6.86 (t, J = 7.5 Hz, 2H), 5.86 (app s, 2H), 6.21 s, 2 H), 7.04 (d, J = 7.5 Hz, 2 H);

13C NMR (CDCl3, 75 MHz) δ 25.70, 27.91, 55.34, 107.11, 107.24, 109.75, 121.50, 123.71, 127.72, 128.18, 141.03, 143.15, 150.82, 176.91; 13 C NMR (CDCl 3 , 75 MHz) δ 25.70, 27.91, 55.34, 107.11, 107.24, 109.75, 121.50, 123.71, 127.72, 128.18, 141.03, 143.15, 150.82, 176.91;

ESIMS m/z 453 [M+H]+.
ESIMS m / z 453 [M + H] &lt; + &gt;.

(2)(2) mesomeso compoundcompound

R f = 0.30 (hexanes/ether, 1:3); white solid, mp 219-220 ℃; R f = 0.30 (hexanes / ether , 1: 3); white solid, mp 219-220 [deg.] C;

IR (KBr) 1703, 1632, 1469 cm-1; IR (KBr) 1703, 1632, 1469 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 2.78 (s, 6H), 3.49 (d, J = 14.1 Hz, 2H), 4.09 (d, J = 14.1 Hz, 2H), 5.57 (d, J = 3.0 Hz, 2H), 5.90 (dd, J = 3.0 and 0.9 Hz, 2H), 6.49 (d, J = 7.8 Hz, 2H), 6.65 (d, J = 7.8 Hz, 2H), 6.79 (t, J = 7.8 Hz, 2H), 6.89 (d, J = 0.9 Hz, 2H), 7.12 (t, J = 7.8 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 2.78 (s, 6H), 3.49 (d, J = 14.1 Hz, 2H), 4.09 (d, J = 14.1 Hz, 2H), 5.57 (d, J = 3.0 Hz (D, J = 7.8 Hz, 2H), 5.90 (dd, J = 3.0 and 0.9 Hz, 2H), 6.49 , 2H), 6.89 (d, J = 0.9 Hz, 2H), 7.12 (t, J = 7.8 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 25.83, 29.58, 56.24, 107.32, 107.72, 109.90, 121.45, 124.45, 128.08, 128.72, 141.10, 144.42, 150.30, 175.79; 13 C NMR (CDCl 3 , 75 MHz) δ 25.83, 29.58, 56.24, 107.32, 107.72, 109.90, 121.45, 124.45, 128.08, 128.72, 141.10, 144.42, 150.30, 175.79;

ESIMS m/z 453 [M+H]+.ESIMS m / z 453 [M + H] &lt; + &gt;.

Anal. Calcd for C28H24N2O4: C, 74.32; H, 5.35;N, 6.19. Anal. Calcd for C28H24N2O4: C, 74.32; H, 5.35; N, 6.19.

Found: C, 74.25; H, 5.46; N, 6.21.
Found: C, 74.25; H, 5.46; N, 6.21.

<< 실시예Example 2-7> 1,1'- 2-7> 1,1'- DimethylDimethyl -3,3'--3,3'- bisbis -(3-- (3- phenylphenyl -- allylallyl )-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 의 제조) -1,3,1 ', 3'-tetrahydro- [3,3'] biindolyl-2,2'-dione

하기 반응식에 따라 Condition B의 조건에서 실시예 1과 동일하게 하여 1,1'-Dimethyl-3,3'-bis-(3-phenyl-allyl)-1,3,1',3'-tetrahydro-[3,3']biindolyl-2,2'-dione 을 합성하였다. D-form 및 L-form 은 36 %, 메조화합물은 35 %의 수율을 나타냈다. 3,3'-bis- (3-phenyl-allyl) -1,3,1 ', 3'-tetrahydrobenzimidazole was prepared in the same manner as in Example 1, [3,3 '] biindolyl-2,2'-dione was synthesized. 36% for D-form and L-form, and 35% for meso compound.

Figure 112014001569291-pat00014
Figure 112014001569291-pat00014

(1)(One) dldl (( enantiomersenantiomers ))

R f = 0.47 (hexanes/ether, 1:3); white solid, mp 221-222 ℃; R f = 0.47 (hexanes / ether , 1: 3); white solid, mp 221-222 [deg.] C;

IR (KBr) 1705, 1611, 1471, 1376 cm-1; IR (KBr) 1705, 1611, 1471, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 3.04 (s, 6H), 3.22 (dd, J = 13.2 and 8.1 Hz, 2H), 3.85 (dd, J = 13.2 and 8.1 Hz, 2H), 5.43 (dt, J = 16.2 and 8.1 Hz, 2H), 6.37 (d, J = 16.2 Hz, 2H), 6.39 (d, J = 7.5 Hz, 2H), 6.84 (t, J = 7.5 Hz, 2H), 6.94-7.22 (m, 14H); 1 H NMR (CDCl 3, 300 MHz) δ 3.04 (s, 6H), 3.22 (dd, J = 13.2 and 8.1 Hz, 2H), 3.85 (dd, J = 13.2 and 8.1 Hz, 2H), 5.43 (dt, J = 16.2 and 8.1 Hz, 2H), 6.37 (d, J = 16.2 Hz, 2H), 6.39 (d, J = 7.5 Hz, 2H), 6.84 (t, J = 7.5 Hz, 2H), 6.94-7.22 m, 14H);

13C NMR (CDCl3, 75 MHz) δ 25.67, 32.52, 56.19, 107.37, 121.78, 123.34, 124.15, 126.04, 126.92, 128.10, 128.21 (2C), 133.70, 137.39, 143.25, 176.92; 13 C NMR (CDCl 3 , 75 MHz) δ 25.67, 32.52, 56.19, 107.37, 121.78, 123.34, 124.15, 126.04, 126.92, 128.10, 128.21 (2C), 133.70, 137.39, 143.25, 176.92;

ESIMS m/z 525 [M+H]+.
ESIMS m / z 525 [M + H] &lt; + &gt;.

(2)(2) mesomeso compoundcompound

R f = 0.19 (hexanes/ether, 1:3); white solid, mp 193-194 ℃; R f = 0.19 (hexanes / ether , 1: 3); white solid, mp 193-194 [deg.] C;

IR (KBr) 1711, 1610, 1470, 1376 cm-1; IR (KBr) 1711, 1610, 1470, 1376 cm &lt; -1 & gt ;;

1H NMR (CDCl3, 300 MHz) δ 2.96 (s, 6H), 3.07 (dd, J = 12.9 and 7.8 Hz, 2H), 3.66 (dd, J = 12.9 and 7.8 Hz, 2H), 5.50 (dt, J = 15.9 and 7.8 Hz, 2H), 6.31 (d, J = 15.9 Hz, 2H), 6.66 (d, J = 7.2 Hz, 2H), 6.70 (d, J = 7.2 Hz, 2H), 6.90 (t, J = 7.2 Hz, 2H), 6.98-7.04 (m, 4H), 7.06-7.20 (m, 6H), 7.23 (t, J = 7.2 Hz, 2H); 1 H NMR (CDCl 3, 300 MHz) δ 2.96 (s, 6H), 3.07 (dd, J = 12.9 and 7.8 Hz, 2H), 3.66 (dd, J = 12.9 and 7.8 Hz, 2H), 5.50 (dt, J = 15.9 and 7.8 Hz, 2H), 6.31 (d, J = 15.9 Hz, 2H), 6.66 (d, J = 7.2 Hz, 2H), 6.70 J = 7.2 Hz, 2H), 6.98-7.04 (m, 4H), 7.06-7.20 (m, 6H), 7.23 (t, J = 7.2 Hz, 2H);

13C NMR (CDCl3, 75 MHz) δ 25.87, 34.06, 56.80, 107.93, 121.60, 123.53, 124.07, 126.04, 127.01, 128.24, 128.39, 128.68, 134.13, 137.28, 144.51, 176.04; 13 C NMR (CDCl 3 , 75 MHz) δ 25.87, 34.06, 56.80, 107.93, 121.60, 123.53, 124.07, 126.04, 127.01, 128.24, 128.39, 128.68, 134.13, 137.28, 144.51, 176.04;

ESIMS m/z 525 [M+H]+.ESIMS m / z 525 [M + H] &lt; + &gt;.

Anal. Calcd for C36H32N2O2: C, 82.41; H, 6.15; N, 5.34. Anal. Calcd for C36H32N2O2: C, 82.41; H, 6.15; N, 5.34.

Found: C, 82.32; H, 6.28; N, 5.19.Found: C, 82.32; H, 6.28; N, 5.19.

Claims (11)

화학식 1로 표시되는 3-알킬 치환 옥시인돌을 준비하는 단계; 및
상기 3-알킬 치환 옥시인돌을 산화제와 유기 용매에 용해시키고 질소 또는 산소 분위기에서 50 내지 150 ℃에서 환류(reflux) 시키면서 반응시키는 단계; 를 포함하고,
상기 산화제는 Copper(II) acetate 및 Silver acetate의 혼합물, 또는 Manganese(III) acetate인 것을 특징으로 하는
아래 화학식 2 또는 화학식 3으로 표시되는 옥시인돌 이합체의 제조 방법.
Figure 112015078028599-pat00015

(상기 화학식 1 내지 3에서, R1 은 벤질, 에틸, 에틸아세테이트, 페녹시에틸, 페닐프로펜 및 퓨라닐메틸 중 어느 하나이고,
R2 는 메틸, 벤질 및 수소 중 어느 하나임)
Preparing a 3-alkyl substituted oxyindole represented by the formula (1); And
Reacting the 3-alkyl-substituted oxyindole with an oxidizing agent and an organic solvent, and refluxing at 50 to 150 ° C in an atmosphere of nitrogen or oxygen; Lt; / RTI &gt;
Wherein the oxidant is a mixture of Copper (II) acetate and Silver acetate, or Manganese (III) acetate.
A process for producing an oxyindole dimer represented by the following general formula (2) or (3).
Figure 112015078028599-pat00015

(Wherein R 1 is any one of benzyl, ethyl, ethyl acetate, phenoxyethyl, phenylpropene, and furanylmethyl,
R &lt; 2 &gt; is either methyl, benzyl or hydrogen)
삭제delete 삭제delete 제 1 항에 있어서,
상기 Copper(II) acetate 는 상기 화학식 1의 화합물 대비 10 내지 30 mol % 포함되고, 상기 Silver acetate 는 1.0 내지 5.0 당량(equiv.) 혼합되는 것을 특징으로 하는 옥시인돌 이합체의 제조 방법.
The method according to claim 1,
Wherein the Copper (II) acetate is contained in an amount of 10 to 30 mol% based on the compound of Formula 1, and the Silver acetate is mixed in an amount of 1.0 to 5.0 equivalent (equiv.).
삭제delete 제 1 항에 있어서,
상기 Manganese(III) acetate 는 1.0 내지 5.0 당량(equiv.) 혼합되는 것을 특징으로 하는 옥시인돌 이합체의 제조 방법.
The method according to claim 1,
The Manganese (III) acetate Is mixed with 1.0 to 5.0 equivalent (equiv.) Of the oxyindole dimer.
제 1 항에 있어서,
상기 유기 용매는 벤젠, 클로로벤젠, 1,2-디클로로벤젠, 또는 이들의 혼합물인 것을 특징으로 하는 옥시인돌 이합체의 제조 방법.
The method according to claim 1,
Wherein the organic solvent is benzene, chlorobenzene, 1,2-dichlorobenzene, or a mixture thereof.
삭제delete 제 1 항에 있어서,
상기 화학식 1로 표시되는 3-알킬 치환 옥시인돌은 하기 화학식 5 내지 7 및 9 내지 12 에서 선택된 어느 하나인 것을 특징으로 하는 옥시인돌 이합체의 제조 방법.
Figure 112016001313841-pat00018

The method according to claim 1,
Wherein the 3-alkyl-substituted oxyindole represented by the formula (1) is any one selected from the following formulas (5) to (7) and (9) to (12).
Figure 112016001313841-pat00018

 삭제delete 삭제delete
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