KR20230071086A - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- KR20230071086A KR20230071086A KR1020220152016A KR20220152016A KR20230071086A KR 20230071086 A KR20230071086 A KR 20230071086A KR 1020220152016 A KR1020220152016 A KR 1020220152016A KR 20220152016 A KR20220152016 A KR 20220152016A KR 20230071086 A KR20230071086 A KR 20230071086A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 800
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- 229910052805 deuterium Inorganic materials 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- KWQNQSDKCINQQP-UHFFFAOYSA-K tri(quinolin-8-yloxy)gallane Chemical compound C1=CN=C2C(O[Ga](OC=3C4=NC=CC=C4C=CC=3)OC=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 KWQNQSDKCINQQP-UHFFFAOYSA-K 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical group CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- Spectroscopy & Molecular Physics (AREA)
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
본 발명은 구동 전압, 효율 및 수명이 개선된 유기 발광 소자에 관한 것이다.The present invention relates to an organic light emitting diode having improved driving voltage, efficiency and lifetime.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.
본 발명은 구동 전압, 효율 및 수명이 개선된 유기 발광 소자에 관한 것이다.The present invention relates to an organic light emitting diode having improved driving voltage, efficiency and lifetime.
본 발명은 하기의 유기 발광 소자를 제공한다:The present invention provides the following organic light emitting device:
양극; anode;
음극; 및cathode; and
상기 양극과 음극 사이의 발광층을 포함하고,Including a light emitting layer between the anode and the cathode,
상기 발광층은 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물을 포함하는,The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.
유기 발광 소자:Organic Light-Emitting Elements:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
X1 내지 X7은 각각 독립적으로, CR1 또는 N이되, X1 내지 X7 중 적어도 하나는 N이고,X 1 to X 7 are each independently CR 1 or N, but at least one of X 1 to X 7 is N;
상기 R1은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,The R 1 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
L1 내지 L3는 각각 독립적으로, 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴렌이고,L 1 to L 3 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
Y1이 N이고, Y2가 O이거나; Y1이 O이고, Y2가 N이고,Y 1 is N and Y 2 is O; Y 1 is O, Y 2 is N,
R' 및 R'1 내지 R'6 중 어느 하나는 하기 화학식 2A로 표시되는 치환기이고, 나머지는 수소; 중수소; 또는 치환 또는 비치환된 C6-60 아릴이고,Any one of R' and R' 1 to R' 6 is a substituent represented by Formula 2A below, and the others are hydrogen; heavy hydrogen; or a substituted or unsubstituted C 6-60 aryl;
[화학식 2A][Formula 2A]
상기 화학식 2A에서,In Formula 2A,
L'1 내지 L'3은 각각 독립적으로, 단일결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L' 1 to L' 3 are each independently a single bond; or a substituted or unsubstituted C 6-60 arylene;
Ar'1 및 Ar'2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이다.Ar' 1 and Ar' 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.
상술한 유기 발광 소자는 발광층에 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물을 포함함으로써, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. The organic light emitting device described above may improve efficiency, low driving voltage, and/or lifetime characteristics of the organic light emitting device by including the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer.
도 1은 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.
도 2는, 기판(1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(7), 발광층(3), 정공저지층(8), 전자 주입 및 수송층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.1 shows an example of an organic light emitting device composed of a
2 shows a
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.
본 명세서에서, 또는 는 다른 치환기에 연결되는 결합을 의미한다. In this specification, or means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 사이클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로아릴기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 치환기가 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 25의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 치환기가 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the ester group may be substituted with an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a substituent of the following structural formula, but is not limited thereto.
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 치환기가 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸, 사이클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우, 등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted, etc. However, it is not limited thereto.
본 명세서에 있어서, 헤테로아릴기는 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로아릴기로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 헤테로아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 헤테로아릴기의 탄소수는 6 내지 20이다. 헤테로아릴기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heteroaryl group is a heteroaryl group containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to one embodiment, the carbon number of the heteroaryl group is 6 to 20. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 헤테로아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기의 예시와 같다. 본 명세서에 있어서, 아릴렌은 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴렌은 2가기인 것을 제외하고는 전술한 헤테로아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 탄화수소 고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 아릴기 또는 사이클로알킬기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴은 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 헤테로아릴기에 관한 설명이 적용될 수 있다.In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heteroaryl group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heteroaryl group described above may be applied except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, heteroaryl is not a monovalent group, and the description of the above-described heteroaryl group may be applied, except that it is formed by combining two substituents.
이하, 각 구성 별로 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail for each configuration.
양극 및 음극anode and cathode
본 발명에서 사용되는 양극 및 음극은, 유기 발광 소자에서 사용되는 전극을 의미한다. An anode and a cathode used in the present invention refer to electrodes used in an organic light emitting device.
상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
정공주입층hole injection layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 양극 상에 정공주입층을 추가로 포함할 수 있다. The organic light emitting device according to the present invention may further include a hole injection layer on the anode, if necessary.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 또한, 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 HOMO 사이인 것이 바람직하다. The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. In addition, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.
정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
정공수송층hole transport layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 양극 상에(또는 정공주입층이 존재하는 경우 정공주입층 상에) 정공수송층을 포함할 수 있다. The organic light emitting device according to the present invention may include a hole transport layer on the anode (or on the hole injection layer if the hole injection layer exists), if necessary.
상기 정공수송층은 양극 또는 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. The hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, it is a material that receives holes from the anode or the hole injection layer and transfers them to the light emitting layer, and has hole mobility. Larger materials are suitable.
상기 정공 수송 물질의 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. Specific examples of the hole transport material include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.
전자차단층electron blocking layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 정공수송층 상에 전자차단층을 포함할 수 있다.The organic light emitting device according to the present invention may include an electron blocking layer on the hole transport layer, if necessary.
상기 전자차단층은 음극에서 주입된 전자가 발광층에서 재결합되지 않고 정공수송층으로 넘어가는 것을 방지하기 위해 정공수송층과 발광층의 사이에 두는 층으로, 전자저지층 또는 전자억제층으로 불리기도 한다. 전자차단층에는 전자수송층보다 전자 친화력이 작은 물질이 바람직하다.The electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer or an electron blocking layer. A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer.
발광층light emitting layer
본 발명에서 사용되는 발광층은, 양극과 음극으로부터 전달받은 정공과 전자를 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 층을 의미한다. 일반적으로, 발광층은 호스트 재료와 도펀트 재료를 포함하며, 본 발명에는 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물을 호스트로 포함한다.The light emitting layer used in the present invention means a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by
바람직하게는, X1 내지 X7 중 어느 하나는 N이고, 나머지는 CR1일 수 있다.Preferably, any one of X 1 to X 7 is N, and the others are CR 1 .
바람직하게는, 상기 화학식 1은 하기 화학식 1-1 내지 화학식 1-7 중 어느 하나로 표시될 수 있다:Preferably,
상기 화학식 1-1 내지 화학식 1-7에서,In Formula 1-1 to Formula 1-7,
R1, L1 내지 L3, Ar1 및 Ar2는 상기 화학식 1에서 정의한 바와 같다.R 1 , L 1 to L 3 , Ar 1 and Ar 2 are as defined in
바람직하게는, R1은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있다. 보다 바람직하게는, R1은 수소, 페닐, 비페닐릴, 나프틸, 카바졸릴, 플루오란테닐, 페난트레닐, 트리페닐레닐, 벤조[a]카바졸릴, 벤조[b]카바졸릴, 벤조[c]카바졸릴, 디벤조퓨라닐, 벤조[d]나프토[1,2-b]퓨라닐, 벤조[d]나프토[2,3-b]퓨라닐, 벤조[d]나프토[2,1-b]퓨라닐, 벤조[d]나프토[1,2-b]티오페닐, 벤조[d]나프토[2,3-b]티오페닐, 벤조[d]나프토[2,1-b]티오페닐, 벤조[c]페난트레닐, 크라이세닐, 페닐 나프틸, 또는 나프틸 페닐이고, 상기 R1이 수소 또는 중수소가 아닌 경우 R1은 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Preferably, R 1 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or it may be a C 2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S. More preferably, R 1 is hydrogen, phenyl, biphenylyl, naphthyl, carbazolyl, fluoranthenyl, phenanthrenyl, triphenylenyl, benzo[a]carbazolyl, benzo[b]carbazolyl, benzo[ c]carbazolyl, dibenzofuranil, benzo[d]naphtho[1,2-b]furanil, benzo[d]naphtho[2,3-b]furanil, benzo[d]naphtho[2 ,1-b] furanyl, benzo [d] naphtho [1,2-b] thiophenyl, benzo [d] naphtho [2,3-b] thiophenyl, benzo [d] naphtho [2,1 -b]thiophenyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, or naphthyl phenyl, wherein R 1 is not hydrogen or deuterium, R 1 may be unsubstituted or substituted with one or more deuterium can
바람직하게는, R1 중 하나는 페닐, 비페닐릴, 나프틸, 카바졸릴, 플루오란테닐, 페난트레닐, 트리페닐레닐, 벤조[a]카바졸릴, 벤조[b]카바졸릴, 벤조[c]카바졸릴, 디벤조퓨라닐, 벤조[d]나프토[1,2-b]퓨라닐, 벤조[d]나프토[2,3-b]퓨라닐, 벤조[d]나프토[2,1-b]퓨라닐, 벤조[d]나프토[1,2-b]티오페닐, 벤조[d]나프토[2,3-b]티오페닐, 벤조[d]나프토[2,1-b]티오페닐, 벤조[c]페난트레닐, 크라이세닐, 페닐 나프틸, 또는 나프틸 페닐이고, 나머지는 수소 또는 중수소이거나, R1은 각각 독립적으로 수소 또는 중수소일 수 있다.Preferably, one of R 1 is phenyl, biphenylyl, naphthyl, carbazolyl, fluoranthenyl, phenanthrenyl, triphenylenyl, benzo[a]carbazolyl, benzo[b]carbazolyl, benzo[c] ]carbazolyl, dibenzofuranil, benzo[d]naphtho[1,2-b]furanil, benzo[d]naphtho[2,3-b]furanyl, benzo[d]naphtho[2, 1-b] furanyl, benzo [d] naphtho [1,2-b] thiophenyl, benzo [d] naphtho [2,3-b] thiophenyl, benzo [d] naphtho [2,1- b]thiophenyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, or naphthyl phenyl, the others being hydrogen or deuterium, or R 1 may each independently be hydrogen or deuterium.
바람직하게는, L1 내지 L3는 각각 독립적으로, 단일결합; 치환 또는 비치환된 C6-20 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴렌일 수 있다. 보다 바람직하게는, L1 내지 L3는 각각 독립적으로, 단일결합, 페닐렌, 나프탈렌디일, , , 또는 이고, 상기 L1 내지 L3가 단일결합이 아닌 경우 L1 내지 L3는 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Preferably, L 1 to L 3 are each independently a single bond; A substituted or unsubstituted C 6-20 arylene; Or it may be a C 2-20 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S. More preferably, L 1 to L 3 are each independently a single bond, phenylene, naphthalenediyl, , , or And, when L 1 to L 3 are not single bonds, L 1 to L 3 may be unsubstituted or substituted with one or more deuterium atoms.
바람직하게는, L1은 단일결합, 나프탈렌디일, , , 또는 이고, L2 및 L3는 각각 독립적으로, 단일결합, 페닐렌, 나프탈렌디일, , , 또는 일 수 있다.Preferably, L 1 is a single bond, naphthalenediyl, , , or And, L 2 and L 3 are each independently a single bond, phenylene, naphthalenediyl, , , or can be
바람직하게는, Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있다. 보다 바람직하게는, Ar1 및 Ar2는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 플루오란테닐, 페난트레닐, 디벤조퓨라닐, 디벤조티오페닐, 크라이세닐, 또는 벤조[c]페난트레닐이고, 상기 Ar1 및 Ar2는 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Preferably, Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-20 aryl; Or it may be a C 2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S. More preferably, Ar 1 and Ar 2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, fluoranthenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, chrysenyl, or Benzo[c]phenanthrenyl, and Ar 1 and Ar 2 may be unsubstituted or substituted with one or more deuterium atoms.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 다음과 같다: Representative examples of the compound represented by
. .
상기 화학식 1로 표시되는 화합물 중 X1이 N이고, X2가 CR1이고, X3 내지 X7이 CH인 경우, 일례로 하기 반응식 1-1과 같은 제조 방법으로 제조할 수 있으며, 화합물 중 X1이 N이고, X2 내지 X7이 CH인 경우, 일례로 하기 반응식 1-2와 같은 제조 방법으로 제조할 수 있고, 외 나머지 화합물도 유사하게 제조할 수 있다.Among the compounds represented by
[반응식 1-1][Scheme 1-1]
[반응식 1-2][Scheme 1-2]
상기 반응식 1-1 및 1-2에서, R1, L1 내지 L3, Ar1 및 Ar2는 상기 화학식 1에서 정의한 바와 같으며, Z1 및 Z2는 각각 독립적으로 할로겐이고, 바람직하게는 Z1 및 Z2는 각각 독립적으로 클로로 또는 브로모이다.In Reaction Schemes 1-1 and 1-2, R 1 , L 1 to L 3 , Ar 1 and Ar 2 are as defined in
상기 반응식 1-1 및 1-2는 스즈키 커플링 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 또한, 필요한 경우 아민 치환 반응이 수반될 수 있으며, 이 경우 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하고, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.Schemes 1-1 and 1-2 are Suzuki coupling reactions, which are preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. In addition, if necessary, an amine substitution reaction may be accompanied, and in this case, it is preferable to carry out the reaction in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.
바람직하게는, R' 및 R'1 내지 R'6 중 어느 하나는 하기 화학식 2A로 표시되는 치환기이고, 나머지는 수소; 중수소; 또는 치환 또는 비치환된 C6-20 아릴일 수 있다. 보다 바람직하게는, R' 및 R'1 내지 R'6 중 어느 하나는 하기 화학식 2A로 표시되는 치환기이고, 나머지는 수소; 중수소; 비치환되거나 1개 내지 5개의 중수소로 치환되는 페닐; 또는 비치환되거나 1개 내지 7개의 중수소로 치환되는 나프틸일 수 있다.Preferably, any one of R' and R' 1 to R' 6 is a substituent represented by the following formula (2A), and the others are hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted C 6-20 aryl. More preferably, any one of R' and R' 1 to R' 6 is a substituent represented by the following formula (2A), and the others are hydrogen; heavy hydrogen; phenyl unsubstituted or substituted with 1 to 5 deuterium; or naphthyl unsubstituted or substituted with 1 to 7 deuterium atoms.
바람직하게는, 상기 화학식 2는 하기 화학식 2-1 또는 화학식 2-2 중 어느 하나로 표시될 수 있다:Preferably,
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 화학식 2-1 및 화학식 2-2에서,In Formula 2-1 and Formula 2-2,
상기 Y1, Y2, R', L'1 내지 L'3, Ar'1 및 Ar'2는 상기 화학식 2에서 정의한 바와 같다.The Y 1 , Y 2 , R', L' 1 to L' 3 , Ar' 1 and Ar' 2 are as defined in
바람직하게는, L'1 내지 L'3은 각각 독립적으로, 단일결합; 또는 치환 또는 비치환된 C6-20 아릴렌일 수 있다. 보다 바람직하게는, L'1 내지 L'3은 각각 독립적으로, 단일결합, 페닐렌, 비페닐디일, 터페닐디일, 나프탈렌디일, , , 또는 이고, 이고, 상기 L'1 내지 L'3이 단일결합이 아닌경우, L'1 내지 L'3은 비치환되거나1개 이상의 중수소로 치환될 수 있다. 보다 바람직하게는, L'1 내지 L'3은 각각 독립적으로, 단일결합, 페닐렌, 비페닐디일, , 나프탈렌디일, , , 또는 이고, 상기 L'1 내지 L'3이 단일결합이 아닌 경우, L'1 내지 L'3은 비치환되거나1개 이상의 중수소로 치환될 수 있다. Preferably, L' 1 to L' 3 are each independently a single bond; Or it may be a substituted or unsubstituted C 6-20 arylene. More preferably, L' 1 to L' 3 are each independently a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthalenediyl, , , or , and , and when L' 1 to L' 3 are not a single bond, L' 1 to L' 3 may be unsubstituted or substituted with one or more deuterium atoms. More preferably, L' 1 to L' 3 are each independently a single bond, phenylene, biphenyldiyl, , naphthalenediyl, , , or And, when L' 1 to L' 3 is not a single bond, L' 1 to L' 3 may be unsubstituted or substituted with one or more deuterium atoms.
바람직하게는, L'1은 단일결합, 페닐렌, 비페닐디일, 나프탈렌디일, 또는 이고, L'2 및 L'3는 각각 독립적으로, 단일결합, 또는 페닐렌일 수 있다.Preferably, L' 1 is a single bond, phenylene, biphenyldiyl, naphthalenediyl, or And, L' 2 and L' 3 may each independently represent a single bond or phenylene.
바람직하게는, Ar'1 및 Ar'2는 각각 독립적으로, 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있다. 보다 바람직하게는, Ar'1 및 Ar'2는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난트레닐, 디벤조퓨라닐, 디벤조티오페닐, 디메틸플루오레닐, 카바졸릴, 또는 페닐 카바졸릴이고, 상기 Ar'1 및 Ar'2는 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Preferably, Ar' 1 and Ar' 2 are each independently a substituted or unsubstituted C 6-20 aryl; Or it may be a C 2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S. More preferably, Ar' 1 and Ar' 2 are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, carba zolyl or phenyl carbazolyl, wherein Ar' 1 and Ar' 2 may be unsubstituted or substituted with one or more deuterium atoms.
상기 화학식 2로 표시되는 화합물의 대표적인 예는 다음과 같다: Representative examples of the compound represented by
. .
상기 화학식 2 표시되는 화합물 중 L'1이 단일결합이 아니고, R'가 화학식 2A인 경우, 일례로 하기 반응식 2-1과 같은 제조 방법으로 제조할 수 있으며, L'1이 단일결합이고, R'가 화학식 2A인 경우, 일례로 하기 반응식 2-2와 같은 제조 방법으로 그 외 나머지 화합물도 유사하게 제조할 수 있다.Among the compounds represented by
[반응식 2-1][Scheme 2-1]
[반응식 2-2][Scheme 2-2]
상기 반응식 2-1 및 2-2에서, R'1 내지 R'6, Y1, Y2, L'1 내지 L'3, Ar'1 및 Ar'2는 상기 화학식 1에서 정의한 바와 같으며, Z'1 및 Z'2는 각각 독립적으로 할로겐이고, 바람직하게는 Z1 및 Z2는 각각 독립적으로 클로로 또는 브로모이다.In Schemes 2-1 and 2-2, R' 1 to R' 6 , Y 1 , Y 2 , L' 1 to L' 3 , Ar' 1 and Ar' 2 are as defined in
상기 반응식 2-1은 스즈키 커플링 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 또한, 상기 반응식 2-2는 아민 치환 반응으로, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하고, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.Reaction Scheme 2-1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction may be modified as known in the art. In addition, Reaction Scheme 2-2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.
바람직하게는, 상기 발광층에서 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물의 중량비는 10:90 내지 90:10일 수 있고, 보다 바람직하게는 20:80 내지 80:20, 30:70 내지 70:30 또는 40:60 내지 60:40일 수 있다. Preferably, the weight ratio of the compound represented by
한편, 상기 발광층은 호스트 외에 도펀트를 추가로 포함할 수 있다. 상기 도펀트 재료로는 유기 발광 소자에 사용되는 물질이면 특별히 제한되지 않는다. 일례로, 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다. 일례로, 하기 군으로부터 선택되는 어느 하나 이상이 도펀트 재료로 사용될 수 있으나, 이에 한정되지 않는다:Meanwhile, the light emitting layer may further include a dopant in addition to a host. The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. For example, there are aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes. For example, one or more selected from the following group may be used as a dopant material, but is not limited thereto:
. .
정공저지층hole blocking layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 발광층 상에 전자수송층을 포함할 수 있다. The organic light emitting device according to the present invention may include an electron transport layer on the light emitting layer, if necessary.
상기 정공저지층은 양극에서 주입된 정공이 발광층에서 재결합되지 않고 전자수송층으로 넘어가는 것을 방지하기 위해 전자수송층과 발광층의 사이에 두는 층으로, 정공억제층, 정공차단층으로 불리기도 한다. 정공저지층에는 이온화에너지가 큰 물질이 바람직하다.The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent holes injected from the anode from passing to the electron transport layer without recombination in the light emitting layer, and is also called a hole blocking layer or a hole blocking layer. A material having high ionization energy is preferred for the hole-blocking layer.
전자수송층electron transport layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 발광층(또는 정공저지층) 상에 전자수송층을 포함할 수 있다. The organic light emitting device according to the present invention may include an electron transport layer on the light emitting layer (or hole blocking layer), if necessary.
상기 전자수송층은, 음극 또는 음극 상에 형성된 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하고, 또한 발광층에서 정공이 전달되는 것을 억제하는 층으로, 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다.The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode. As a material that can be received and transferred to the light emitting layer, a material having high electron mobility is suitable.
상기 전자 수송 물질의 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.Specific examples of the electron transport material include Al complexes of 8-hydroxyquinoline; Complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.
전자주입층electron injection layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 발광층 상에(또는 전자주송층이 존재하는 경우 전자수송층 상에) 전자주입층을 추가로 포함할 수 있다. The organic light emitting device according to the present invention may further include an electron injection layer on the light emitting layer (or on the electron transport layer when the electron transport layer is present), if necessary.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물을 사용하는 것이 바람직하다. The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. It is preferable to use a compound that prevents migration to a layer and has excellent thin film forming ability.
상기 전자주입층으로 사용될 수 있는 물질의 구체적인 예로는, 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다. Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preore nylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
유기 발광 소자organic light emitting device
본 발명에 따른 유기 발광 소자의 구조를 도 1 및 도 2에 예시하였다. 도 1은, 기판(1), 양극(2), 발광층(3), 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 도 2는, 기판(1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(7), 발광층(3), 정공저지층(8), 전자 주입 및 수송층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 . 1 shows an example of an organic light emitting device composed of a
본 발명에 따른 유기 발광 소자는 상술한 구성을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 상술한 각 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 상술한 구성의 역순으로 양극 물질까지 차례로 증착시켜 유기 발광 소자를 만들 수 있다(WO 2003/012890). 또한, 발광층은 호스트 및 도펀트를 진공 증착법 뿐만 아니라 용액 도포법에 의하여 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-described layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
한편, 본 발명에 따른 유기 발광 소자는 배면 발광(bottom emission) 소자, 전면 발광(top emission) 소자, 또는 양면 발광 소자일 수 있으며, 특히 상대적으로 높은 발광 효율이 요구되는 배면 발광 소자일 수 있다.Meanwhile, the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.
합성예 1-1Synthesis Example 1-1
화합물 A(15 g, 45.5 mmol)와 화합물 Trz1(15.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subA-1를 13.9 g 제조하였다.(수율 63%, MS: [M+H]+= 485)Compound A (15 g, 45.5 mmol) and compound Trz1 (15.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subA-1. (Yield 63%, MS: [M+H] + = 485)
화합물 subA-1(15 g, 30.9 mmol)와 화합물 sub1(7.2 g, 32.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(12.8 g, 92.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1 11.6 g 제조하였다.(수율 60%, MS: [M+H]+= 627)Compound subA-1 (15 g, 30.9 mmol) and compound sub1 (7.2 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.8 g, 92.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of Compound 1-1. (Yield 60%, MS: [M+H] + = 627)
합성예 1-2Synthesis Example 1-2
화합물 B(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subB-1를 13.6 g 제조하였다.(수율 69%, MS: [M+H]+= 435)Compound B (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound subB-1. (Yield 69%, MS: [M+H] + = 435)
화합물 subB-1(15 g, 34.5 mmol)와 화합물 sub2(9.9 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-2 14.5 g 제조하였다.(수율 67%, MS: [M+H]+= 627)Compound subB-1 (15 g, 34.5 mmol) and compound sub2 (9.9 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of Compound 1-2. (Yield 67%, MS: [M+H] + = 627)
합성예 1-3Synthesis Example 1-3
화합물 C(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subC-1를 12.6 g 제조하였다.(수율 64%, MS: [M+H]+= 435)Compound C (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound subC-1. (Yield 64%, MS: [M+H] + = 435)
화합물 subC-1(15 g, 34.5 mmol)와 화합물 sub3(8.9 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-3 14.1 g 제조하였다.(수율 68%, MS: [M+H]+= 601)Compound subC-1 (15 g, 34.5 mmol) and compound sub3 (8.9 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of Compound 1-3. (Yield 68%, MS: [M+H] + = 601)
합성예 1-4Synthesis Example 1-4
화합물 D(15 g, 45.5 mmol)와 화합물 Trz3(21.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subD-1를 21.1 g 제조하였다.(수율 76%, MS: [M+H]+= 611)Compound D (15 g, 45.5 mmol) and compound Trz3 (21.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.1 g of compound subD-1. (Yield 76%, MS: [M+H] + = 611)
화합물 subD-1(15 g, 24.5 mmol)와 화합물 sub4(3.1 g, 25.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(10.2 g, 73.6 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-4 12.8 g 제조하였다.(수율 80%, MS: [M+H]+= 653)Compound subD-1 (15 g, 24.5 mmol) and compound sub4 (3.1 g, 25.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.6 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of Compound 1-4. (Yield 80%, MS: [M+H] + = 653)
합성예 1-5Synthesis Example 1-5
화합물 E(15 g, 50.8 mmol)와 화합물 Trz4(25 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-5를 20.4 g 제조하였다.(수율 67%, MS: [M+H]+= 601)Compound E (15 g, 50.8 mmol) and compound Trz4 (25 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound 1-5. (Yield 67%, MS: [M+H] + = 601)
합성예 1-6Synthesis Example 1-6
화합물 E(15 g, 50.8 mmol)와 화합물 Trz5(25.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-6을 20.4 g 제조하였다.(수율 65%, MS: [M+H]+= 617)Compound E (15 g, 50.8 mmol) and compound Trz5 (25.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of compound 1-6. (Yield 65%, MS: [M+H] + = 617)
합성예 1-7Synthesis Example 1-7
화합물 E(15 g, 50.8 mmol)와 화합물 Trz6(28.5 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-7 20.7 g 제조하였다.(수율 61%, MS: [M+H]+= 667)Compound E (15 g, 50.8 mmol) and compound Trz6 (28.5 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.7 g of Compound 1-7. (Yield 61%, MS: [M+H] + = 667)
합성예 1-8Synthesis Example 1-8
화합물 E(15 g, 50.8 mmol)와 화합물 Trz7(26.4 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-8을 24.2 g 제조하였다.(수율 76%, MS: [M+H]+= 627)Compound E (15 g, 50.8 mmol) and compound Trz7 (26.4 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.2 g of compound 1-8. (Yield 76%, MS: [M+H] + = 627)
합성예 1-9Synthesis Example 1-9
화합물 F(15 g, 45.5 mmol)와 화합물 Trz8(19.5 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subF-1를 17 g 제조하였다.(수율 65%, MS: [M+H]+= 575)Compound F (15 g, 45.5 mmol) and compound Trz8 (19.5 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17 g of compound subF-1. (Yield 65%, MS: [M+H] + = 575)
화합물 subF-1(15 g, 26.1 mmol)와 화합물 sub4(3.3 g, 27.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(10.8 g, 78.3 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-9 12.9 g 제조하였다.(수율 80%, MS: [M+H]+= 617)Compound subF-1 (15 g, 26.1 mmol) and compound sub4 (3.3 g, 27.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.8 g, 78.3 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 1-9. (Yield 80%, MS: [M+H] + = 617)
합성예 1-10Synthesis Example 1-10
화합물 G(15 g, 45.5 mmol)와 화합물 Trz9(20.7 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subG-1를 21.9 g 제조하였다.(수율 80%, MS: [M+H]+= 601)Compound G (15 g, 45.5 mmol) and compound Trz9 (20.7 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.9 g of compound subG-1. (Yield 80%, MS: [M+H] + = 601)
화합물 subG-1(15 g, 25 mmol)와 화합물 sub5(4.5 g, 26.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(10.3 g, 74.9 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-10 13 g 제조하였다.(수율 75%, MS: [M+H]+= 693)Compound subG-1 (15 g, 25 mmol) and compound sub5 (4.5 g, 26.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.3 g, 74.9 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of Compound 1-10. (Yield 75%, MS: [M+H] + = 693)
합성예 1-11Synthesis Example 1-11
화합물 G(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subG-2를 13.8 g 제조하였다.(수율 70%, MS: [M+H]+= 435)Compound G (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound subG-2. (Yield 70%, MS: [M+H] + = 435)
화합물 subG-2(15 g, 34.5 mmol)와 화합물 sub6(17.5 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-11 14 g 제조하였다.(수율 65%, MS: [M+H]+= 627)Compound subG-2 (15 g, 34.5 mmol) and compound sub6 (17.5 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of Compound 1-11. (Yield 65%, MS: [M+H] + = 627)
합성예 1-12Synthesis Example 1-12
화합물 G(15 g, 45.5 mmol)와 화합물 Trz10(16.4 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subG-3를 14.2 g 제조하였다.(수율 61%, MS: [M+H]+= 511)Compound G (15 g, 45.5 mmol) and compound Trz10 (16.4 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound subG-3. (Yield 61%, MS: [M+H] + = 511)
질소 분위기에서 화합물 subG-3(10 g, 19.6 mmol), 화합물 sub7(4.3 g, 20 mmol), sodium tert-butoxide(2.4 g, 25.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-12 9.5g 을 얻었다.(수율 70%, MS: [M+H]+= 692)In a nitrogen atmosphere, compound subG-3 (10 g, 19.6 mmol), compound sub7 (4.3 g, 20 mmol), and sodium tert-butoxide (2.4 g, 25.4 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound 1-12. (Yield 70%, MS: [M+H] + = 692)
합성예 1-13Synthesis Example 1-13
화합물 H(15 g, 45.5 mmol)와 화합물 Trz11(17.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subH-1를 16.2 g 제조하였다.(수율 68%, MS: [M+H]+= 525)Compound H (15 g, 45.5 mmol) and compound Trz11 (17.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound subH-1. (Yield 68%, MS: [M+H] + = 525)
화합물 subH-1(15 g, 28.6 mmol)와 화합물 sub5(5.2 g, 30 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.8 g, 85.7 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-13 10.9 g 제조하였다.(수율 62%, MS: [M+H]+= 617)Compound subH-1 (15 g, 28.6 mmol) and compound sub5 (5.2 g, 30 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8 g, 85.7 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of Compound 1-13. (Yield 62%, MS: [M+H] + = 617)
합성예 1-14Synthesis Example 1-14
화합물 I(15 g, 50.8 mmol)와 화합물 Trz12(23.7 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-14 17.6 g 제조하였다.(수율 60%, MS: [M+H]+= 577)Compound I (15 g, 50.8 mmol) and compound Trz12 (23.7 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.6 g of Compound 1-14. (Yield 60%, MS: [M+H] + = 577)
합성예 1-15Synthesis Example 1-15
화합물 I(15 g, 50.8 mmol)와 화합물 Trz13(25 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-15 21.7 g 제조하였다.(수율 71%, MS: [M+H]+= 601)Compound I (15 g, 50.8 mmol) and compound Trz13 (25 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.7 g of Compound 1-15. (Yield 71%, MS: [M+H] + = 601)
합성예 1-16Synthesis Example 1-16
화합물 I(15 g, 50.8 mmol)와 화합물 Trz14(25.1 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-16 21.4 g 제조하였다.(수율 70%, MS: [M+H]+= 603)Compound I (15 g, 50.8 mmol) and compound Trz14 (25.1 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.4 g of Compound 1-16. (Yield 70%, MS: [M+H] + = 603)
합성예 1-17Synthesis Example 1-17
화합물 J(15 g, 45.5 mmol)와 화합물 Trz15(17.6 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subJ-1를 15.6 g 제조하였다.(수율 64%, MS: [M+H]+= 535)Compound J (15 g, 45.5 mmol) and compound Trz15 (17.6 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound subJ-1. (Yield 64%, MS: [M+H] + = 535)
화합물 subJ-1(15 g, 28 mmol)와 화합물 sub5(5.1 g, 29.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.6 g, 84.1 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-17 13.7 g 제조하였다.(수율 78%, MS: [M+H]+= 627)Compound subJ-1 (15 g, 28 mmol) and compound sub5 (5.1 g, 29.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.6 g, 84.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of Compound 1-17. (Yield 78%, MS: [M+H] + = 627)
합성예 1-18Synthesis Example 1-18
화합물 K(15 g, 45.5 mmol)와 화합물 Trz1(15.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subK-1를 13.9 g 제조하였다.(수율 63%, MS: [M+H]+= 485)Compound K (15 g, 45.5 mmol) and compound Trz1 (15.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subK-1. (Yield 63%, MS: [M+H] + = 485)
화합물 subK-1(15 g, 30.9 mmol)와 화합물 sub8(6.9 g, 32.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(12.8 g, 92.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-18 12.4 g 제조하였다.(수율 65%, MS: [M+H]+= 617)Compound subK-1 (15 g, 30.9 mmol) and compound sub8 (6.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.8 g, 92.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of Compound 1-18. (Yield 65%, MS: [M+H] + = 617)
합성예 1-19Synthesis Example 1-19
화합물 L(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subL-1를 13.6 g 제조하였다.(수율 69%, MS: [M+H]+= 435)Compound L (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound subL-1. (Yield 69%, MS: [M+H] + = 435)
화합물 subL-1(15 g, 34.5 mmol)와 화합물 sub9(8.9 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-19를 13.2 g 제조하였다.(수율 64%, MS: [M+H]+= 601)Compound subL-1 (15 g, 34.5 mmol) and compound sub9 (8.9 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound 1-19. (Yield 64%, MS: [M+H] + = 601)
합성예 1-20Synthesis Example 1-20
화합물 subL-1(15 g, 34.5 mmol)와 화합물 sub10(10.1 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-20을 14.4 g 제조하였다.(수율 66%, MS: [M+H]+= 633)Compound subL-1 (15 g, 34.5 mmol) and compound sub10 (10.1 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 1-20. (Yield 66%, MS: [M+H] + = 633)
합성예 1-21Synthesis Example 1-21
화합물 K(15 g, 45.5 mmol)와 화합물 Trz16(17.9 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subK-2를 16.7 g 제조하였다.(수율 68%, MS: [M+H]+= 541)Compound K (15 g, 45.5 mmol) and compound Trz16 (17.9 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound subK-2. (Yield 68%, MS: [M+H] + = 541)
질소 분위기에서 화합물 subK-2(10 g, 18.5 mmol), 화합물 sub11(3.2 g, 18.9 mmol), sodium tert-butoxide(2.3 g, 24 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-21 7.8 g을 얻었다.(수율 63%, MS: [M+H]+= 672)In a nitrogen atmosphere, compound subK-2 (10 g, 18.5 mmol), compound sub11 (3.2 g, 18.9 mmol), and sodium tert-butoxide (2.3 g, 24 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of compound 1-21. (Yield 63%, MS: [M+H] + = 672)
합성예 1-22Synthesis Example 1-22
화합물 K(15 g, 45.5 mmol)와 화합물 Trz17(16.4 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subK-3를 15.3 g 제조하였다.(수율 66%, MS: [M+H]+= 511)Compound K (15 g, 45.5 mmol) and compound Trz17 (16.4 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound subK-3. (Yield 66%, MS: [M+H] + = 511)
화합물 subK-3(15 g, 29.4 mmol)와 화합물 sub5(5.3 g, 30.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(12.2 g, 88.1 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-22를 13.8 g 제조하였다.(수율 78%, MS: [M+H]+= 603)Compound subK-3 (15 g, 29.4 mmol) and compound sub5 (5.3 g, 30.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.2 g, 88.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound 1-22. (Yield 78%, MS: [M+H] + = 603)
합성예 1-23Synthesis Example 1-23
화합물 M(15 g, 50.8 mmol)와 화합물 Trz18(25.1 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-23 19.9 g 제조하였다.(수율 65%, MS: [M+H]+= 603)Compound M (15 g, 50.8 mmol) and compound Trz18 (25.1 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.9 g of Compound 1-23. (Yield 65%, MS: [M+H] + = 603)
합성예 1-24Synthesis Example 1-24
화합물 M(15 g, 50.8 mmol)와 화합물 Trz19(25 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-24를 20.4 g 제조하였다.(수율 67%, MS: [M+H]+= 601)Compound M (15 g, 50.8 mmol) and compound Trz19 (25 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound 1-24. (Yield 67%, MS: [M+H] + = 601)
합성예 1-25Synthesis Example 1-25
화합물 M(15 g, 50.8 mmol)와 화합물 Trz20(25.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-25 19.7 g 제조하였다.(수율 63%, MS: [M+H]+= 617)Compound M (15 g, 50.8 mmol) and compound Trz20 (25.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of Compound 1-25. (Yield 63%, MS: [M+H] + = 617)
합성예 1-26Synthesis Example 1-26
화합물 N(15 g, 45.5 mmol)와 화합물 Trz1(15.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subN-1를 15.9 g 제조하였다.(수율 72%, MS: [M+H]+= 485)Compound N (15 g, 45.5 mmol) and compound Trz1 (15.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of compound subN-1. (Yield 72%, MS: [M+H] + = 485)
화합물 subN-1(15 g, 30.9 mmol)와 화합물 sub5(5.6 g, 32.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(12.8 g, 92.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-26을 12.7 g 제조하였다.(수율 71%, MS: [M+H]+= 577)Compound subN-1 (15 g, 30.9 mmol) and compound sub5 (5.6 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.8 g, 92.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound 1-26. (Yield 71%, MS: [M+H] + = 577)
합성예 1-27Synthesis Example 1-27
화합물 O(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subO-1을 15 g 제조하였다.(수율 76%, MS: [M+H]+= 435)Compound O (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound subO-1. (Yield 76%, MS: [M+H] + = 435)
화합물 subO-1(15 g, 34.5 mmol)와 화합물 sub12(9.9 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-27을 15.8 g 제조하였다.(수율 73%, MS: [M+H]+= 627)Compound subO-1 (15 g, 34.5 mmol) and compound sub12 (9.9 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 g of compound 1-27. (Yield 73%, MS: [M+H] + = 627)
합성예 1-28Synthesis Example 1-28
화합물 N(15 g, 45.5 mmol)와 화합물 Trz8(12.8 g, 47.8 mmol)을 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subN-2를 20.4 g 제조하였다.(수율 78%, MS: [M+H]+= 575)Compound N (15 g, 45.5 mmol) and compound Trz8 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound subN-2. (Yield 78%, MS: [M+H] + = 575)
화합물 subN-2(15 g, 26.1 mmol)와 화합물 sub13(5.4 g, 27.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(10.8 g, 78.3 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-28을 10.8 g 제조하였다.(수율 60%, MS: [M+H]+= 693)Compound subN-2 (15 g, 26.1 mmol) and compound sub13 (5.4 g, 27.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.8 g, 78.3 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound 1-28. (Yield 60%, MS: [M+H] + = 693)
합성예 1-29Synthesis Example 1-29
화합물 P(15 g, 45.5 mmol)와 화합물 Trz1(15.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subP-1를 13.7 g 제조하였다.(수율 62%, MS: [M+H]+= 485)Compound P (15 g, 45.5 mmol) and compound Trz1 (15.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound subP-1. (Yield 62%, MS: [M+H] + = 485)
질소 분위기에서 화합물 subP-1(10 g, 20.6 mmol), 화합물 sub11(3.5 g, 21 mmol), sodium tert-butoxide(2.6 g, 26.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입했다. 4 시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-29를 6.5 g을 얻었다.(수율 51%, MS: [M+H]+= 616)In a nitrogen atmosphere, compound subP-1 (10 g, 20.6 mmol), compound sub11 (3.5 g, 21 mmol), and sodium tert-butoxide (2.6 g, 26.8 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 1-29. (Yield 51%, MS: [M+H] + = 616)
합성예 1-30Synthesis Example 1-30
화합물 Q(15 g, 45.5 mmol)와 화합물 Trz21(17.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subQ-1를 16.5 g 제조하였다.(수율 69%, MS: [M+H]+= 525)Compound Q (15 g, 45.5 mmol) and compound Trz21 (17.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of compound subQ-1. (Yield 69%, MS: [M+H] + = 525)
화합물 subQ-1(15 g, 28.6 mmol)와 화합물 sub14(5.9 g, 30 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.8 g, 85.7 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-30을 14.7 g 제조하였다.(수율 80%, MS: [M+H]+= 643)Compound subQ-1 (15 g, 28.6 mmol) and compound sub14 (5.9 g, 30 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.8 g, 85.7 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-30. (Yield 80%, MS: [M+H] + = 643)
합성예 1-31Synthesis Example 1-31
화합물 R(15 g, 50.8 mmol)와 화합물 Trz22(23.7 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-31을 18.7 g 제조하였다.(수율 64%, MS: [M+H]+= 577)Compound R (15 g, 50.8 mmol) and compound Trz22 (23.7 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.7 g of compound 1-31. (Yield 64%, MS: [M+H] + = 577)
합성예 1-32Synthesis Example 1-32
화합물 R(15 g, 50.8 mmol)와 화합물 Trz23(23.6 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-32를 23.1 g 제조하였다.(수율 79%, MS: [M+H]+= 575)Compound R (15 g, 50.8 mmol) and compound Trz23 (23.6 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.1 g of Compound 1-32. (Yield 79%, MS: [M+H] + = 575)
합성예 1-33Synthesis Example 1-33
화합물 R(15 g, 50.8 mmol)와 화합물 Trz24(29.9 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-33을 26 g 제조하였다.(수율 74%, MS: [M+H]+= 693)Compound R (15 g, 50.8 mmol) and compound Trz24 (29.9 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 1-33. (Yield 74%, MS: [M+H] + = 693)
합성예 1-34Synthesis Example 1-34
화합물 S(15 g, 45.5 mmol)와 화합물 Trz15(17.6 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subS-1를 19 g 제조하였다.(수율 78%, MS: [M+H]+= 535)Compound S (15 g, 45.5 mmol) and compound Trz15 (17.6 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound subS-1. (Yield 78%, MS: [M+H] + = 535)
화합물 subS-1(15 g, 28 mmol)와 화합물 sub15(6.5 g, 29.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.6 g, 84.1 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-34를 13.3 g 제조하였다.(수율 70%, MS: [M+H]+= 677)Compound subS-1 (15 g, 28 mmol) and compound sub15 (6.5 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.6 g, 84.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-34. (Yield 70%, MS: [M+H] + = 677)
합성예 1-35Synthesis Example 1-35
화합물 T(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subT-1를 14.4 g 제조하였다.(수율 73%, MS: [M+H]+= 435)Compound T (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.4 g of compound subT-1. (Yield 73%, MS: [M+H] + = 435)
화합물 subT-1(15 g, 34.5 mmol)와 화합물 sub16(9.5 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-35를 17 g 제조하였다.(수율 80%, MS: [M+H]+= 617)Compound subT-1 (15 g, 34.5 mmol) and compound sub16 (9.5 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of compound 1-35. (Yield 80%, MS: [M+H] + = 617)
합성예 1-36Synthesis Example 1-36
화합물 S(15 g, 45.5 mmol)와 화합물 Trz25(18.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subS-2를 19.6 g 제조하였다.(수율 77%, MS: [M+H]+= 561)Compound S (15 g, 45.5 mmol) and compound Trz25 (18.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.6 g of compound subS-2. (Yield 77%, MS: [M+H] + = 561)
질소 분위기에서 화합물 subS-2(10 g, 17.8 mmol), 화합물 sub17(4 g, 18.2 mmol), sodium tert-butoxide(2.2 g, 23.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol)을 투입했다. 5 시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-36 7.3g 을 얻었다.(수율 55%, MS: [M+H]+= 742)In a nitrogen atmosphere, compound subS-2 (10 g, 17.8 mmol), compound sub17 (4 g, 18.2 mmol), and sodium tert-butoxide (2.2 g, 23.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 1-36. (Yield 55%, MS: [M+H] + = 742)
합성예 1-37Synthesis Example 1-37
화합물 U(15 g, 45.5 mmol)와 화합물 Trz26(17.9 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subU-1를 18.7 g 제조하였다.(수율 76%, MS: [M+H]+= 541)Compound U (15 g, 45.5 mmol) and compound Trz26 (17.9 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.7 g of compound subU-1. (Yield 76%, MS: [M+H] + = 541)
화합물 subU-1(15 g, 27.7 mmol)와 화합물 sub18(6.6 g, 29.1 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.5 g, 83.2 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-37을 13.5 g 제조하였다.(수율 71%, MS: [M+H]+= 689)Compound subU-1 (15 g, 27.7 mmol) and compound sub18 (6.6 g, 29.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.5 g, 83.2 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound 1-37. (Yield 71%, MS: [M+H] + = 689)
합성예 1-38Synthesis Example 1-38
화합물 V(15 g, 50.8 mmol)와 화합물 Trz27(22.3 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-38을 16.8 g 제조하였다.(수율 60%, MS: [M+H]+= 551)Compound V (15 g, 50.8 mmol) and compound Trz27 (22.3 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.8 g of compound 1-38. (Yield 60%, MS: [M+H] + = 551)
합성예 1-39Synthesis Example 1-39
화합물 V(15 g, 50.8 mmol)와 화합물 Trz28(23.2 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-39를 20.1 g 제조하였다.(수율 70%, MS: [M+H]+= 567)Compound V (15 g, 50.8 mmol) and compound Trz28 (23.2 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of Compound 1-39. (Yield 70%, MS: [M+H] + = 567)
합성예 1-40Synthesis Example 1-40
화합물 V(15 g, 50.8 mmol)와 화합물 Trz29(30.4 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-40을 24.6 g 제조하였다.(수율 69%, MS: [M+H]+= 703)Compound V (15 g, 50.8 mmol) and compound Trz29 (30.4 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of compound 1-40. (Yield 69%, MS: [M+H] + = 703)
합성예 1-41Synthesis Example 1-41
화합물 V(15 g, 50.8 mmol)와 화합물 Trz30(25.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-41 23.8 g 제조하였다.(수율 76%, MS: [M+H]+= 617)Compound V (15 g, 50.8 mmol) and compound Trz30 (25.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.8 g of Compound 1-41. (Yield 76%, MS: [M+H] + = 617)
합성예 1-42Synthesis Example 1-42
화합물 W(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subW-1를 13 g 제조하였다.(수율 66%, MS: [M+H]+= 435)Compound W (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of compound subW-1. (Yield 66%, MS: [M+H] + = 435)
화합물 subW-1(15 g, 34.5 mmol)와 화합물 sub19(9.9 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-42를 16.4 g 제조하였다.(수율 76%, MS: [M+H]+= 627)Compound subW-1 (15 g, 34.5 mmol) and compound sub19 (9.9 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of compound 1-42. (Yield 76%, MS: [M+H] + = 627)
합성예 1-43Synthesis Example 1-43
화합물 X(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subX-1를 14 g 제조하였다.(수율 71%, MS: [M+H]+= 435)Compound X (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound subX-1. (Yield 71%, MS: [M+H] + = 435)
화합물 subX-1(15 g, 34.5 mmol)와 화합물 sub20(10.1 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-43 14 g 제조하였다.(수율 64%, MS: [M+H]+= 633)Compound subX-1 (15 g, 34.5 mmol) and compound sub20 (10.1 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-43. (Yield 64%, MS: [M+H] + = 633)
합성예 1-44Synthesis Example 1-44
화합물 Y(15 g, 45.5 mmol)와 화합물 Trz2(12.6 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subY-1를 15.8 g 제조하였다.(수율 80%, MS: [M+H]+= 435)Compound Y (15 g, 45.5 mmol) and compound Trz2 (12.6 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 g of compound subY-1. (Yield 80%, MS: [M+H] + = 435)
화합물 subY-1(15 g, 34.5 mmol)와 화합물 sub21(9.5 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-44를 14.9 g 제조하였다.(수율 70%, MS: [M+H]+= 617)Compound subY-1 (15 g, 34.5 mmol) and compound sub21 (9.5 g, 36.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of Compound 1-44. (Yield 70%, MS: [M+H] + = 617)
합성예 1-45Synthesis Example 1-45
화합물 X(15 g, 45.5 mmol)와 화합물 Trz31(18.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subX-2를 18.1 g 제조하였다.(수율 71%, MS: [M+H]+= 561)Compound X (15 g, 45.5 mmol) and compound Trz31 (18.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.1 g of compound subX-2. (Yield 71%, MS: [M+H] + = 561)
화합물 subX-2(15 g, 26.7 mmol)와 화합물 sub22(7.6 g, 28.1 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.1 g, 80.2 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-45를 15.7 g 제조하였다.(수율 78%, MS: [M+H]+= 753)Compound subX-2 (15 g, 26.7 mmol) and compound sub22 (7.6 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.2 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound 1-45. (Yield 78%, MS: [M+H] + = 753)
합성예 1-46Synthesis Example 1-46
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz32(21 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-46 16.6 g 제조하였다.(수율 62%, MS: [M+H]+= 527)Compound Z (15 g, 50.8 mmol) and compound Trz32 (21 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.6 g of Compound 1-46. (Yield 62%, MS: [M+H] + = 527)
합성예 1-47Synthesis Example 1-47
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz33(22.3 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-47 19.3 g 제조하였다.(수율 69%, MS: [M+H]+= 551)Compound Z (15 g, 50.8 mmol) and compound Trz33 (22.3 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.3 g of Compound 1-47. (Yield 69%, MS: [M+H] + = 551)
합성예 1-48Synthesis Example 1-48
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz34(25.7 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-48 23.1 g 제조하였다.(수율 74%, MS: [M+H]+= 615)Compound Z (15 g, 50.8 mmol) and compound Trz34 (25.7 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.1 g of Compound 1-48. (Yield 74%, MS: [M+H] + = 615)
합성예 1-49Synthesis Example 1-49
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz35(25.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-49 22.9 g 제조하였다.(수율 73%, MS: [M+H]+= 617)Compound Z (15 g, 50.8 mmol) and compound Trz35 (25.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.9 g of Compound 1-49. (Yield 73%, MS: [M+H] + = 617)
합성예 1-50Synthesis Example 1-50
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz36(25.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-50 19.4 g 제조하였다.(수율 62%, MS: [M+H]+= 617)Compound Z (15 g, 50.8 mmol) and compound Trz36 (25.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4 g of Compound 1-50. (Yield 62%, MS: [M+H] + = 617)
합성예 1-51Synthesis Example 1-51
화합물 Z(15 g, 50.8 mmol)와 화합물 Trz37(27.8 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-51 19.9 g 제조하였다.(수율 60%, MS: [M+H]+= 653)Compound Z (15 g, 50.8 mmol) and compound Trz37 (27.8 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of Compound 1-51. (Yield 60%, MS: [M+H] + = 653)
합성예 1-52Synthesis Example 1-52
화합물 AA(15 g, 45.5 mmol)와 화합물 Trz1(15.2 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subAA-1를 17.2 g 제조하였다.(수율 78%, MS: [M+H]+= 485)Compound AA (15 g, 45.5 mmol) and compound Trz1 (15.2 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.2 g of compound subAA-1. (Yield 78%, MS: [M+H] + = 485)
화합물 subAA-1(15 g, 30.9 mmol)와 화합물 sub23(7.4 g, 32.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(12.8 g, 92.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-52를 13.9 g 제조하였다.(수율 71%, MS: [M+H]+= 633)Compound subAA-1 (15 g, 30.9 mmol) and compound sub23 (7.4 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.8 g, 92.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of Compound 1-52. (Yield 71%, MS: [M+H] + = 633)
합성예 1-53Synthesis Example 1-53
화합물 AB(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subAB-1를 14 g 제조하였다.(수율 71%, MS: [M+H]+= 435)Compound AB (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14 g of compound subAB-1. (Yield 71%, MS: [M+H] + = 435)
화합물 subAB-1(14 g, 32 mmol), 화합물 sub24(8.9 g, 33.8 mmol) 를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(13.3 g, 96.6 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 5 시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-53을 12.5g 을 얻었다.(수율 62%, MS: [M+H]+= 617)Compound subAB-1 (14 g, 32 mmol) and compound sub24 (8.9 g, 33.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (13.3 g, 96.6 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 1-53. (Yield 62%, MS: [M+H] + = 617)
합성예 1-54Synthesis Example 1-54
화합물 AA(15 g, 45.5 mmol)와 화합물 Trz2(12.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subAA-2를 12.6 g 제조하였다.(수율 64%, MS: [M+H]+= 435)Compound AA (15 g, 45.5 mmol) and compound Trz2 (12.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound subAA-2. (Yield 64%, MS: [M+H] + = 435)
화합물 subAA-2(15 g, 34.5 mmol)와 화합물 sub25(10.1 g, 36.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(14.3 g, 103.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-54를 13.3 g 제조하였다.(수율 61%, MS: [M+H]+= 633)Compound subAA-2 (15 g, 34.5 mmol) and compound sub25 (10.1 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-54. (Yield 61%, MS: [M+H] + = 633)
합성예 1-55Synthesis Example 1-55
화합물 AB(15 g, 45.5 mmol)와 화합물 Trz21(17.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subAB-2를 15.5 g 제조하였다.(수율 65%, MS: [M+H]+= 525)Compound AB (15 g, 45.5 mmol) and compound Trz21 (17.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.5 g of compound subAB-2. (Yield 65%, MS: [M+H] + = 525)
화합물 subAB-2(15 g, 28.6 mmol)와 화합물 sub26(7.4 g, 30 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(11.8 g, 85.7 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-55를 12.5 g 제조하였다.(수율 63%, MS: [M+H]+= 693)Compound subAB-2 (15 g, 28.6 mmol) and compound sub26 (7.4 g, 30 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8 g, 85.7 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound 1-55. (Yield 63%, MS: [M+H] + = 693)
합성예 1-56Synthesis Example 1-56
화합물 AB(15 g, 45.5 mmol)와 화합물 Trz38(20.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 subAB-3을 18.4 g 제조하였다.(수율 69%, MS: [M+H]+= 587)Compound AB (15 g, 45.5 mmol) and compound Trz38 (20.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.4 g of compound subAB-3. (Yield 69%, MS: [M+H] + = 587)
화합물 subAB-3(15 g, 25.6 mmol)과 화합물 sub27(5.7 g, 26.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(10.6 g, 76.7 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-56을 13.4 g 제조하였다.(수율 73%, MS: [M+H]+= 719)Compound subAB-3 (15 g, 25.6 mmol) and compound sub27 (5.7 g, 26.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.6 g, 76.7 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 1-56. (Yield 73%, MS: [M+H] + = 719)
합성예 1-57Synthesis Example 1-57
화합물 AC(15 g, 50.8 mmol)와 화합물 Trz39(22.3 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-57을 22.1 g 제조하였다.(수율 79%, MS: [M+H]+= 551)Compound AC (15 g, 50.8 mmol) and compound Trz39 (22.3 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.1 g of compound 1-57. (Yield 79%, MS: [M+H] + = 551)
합성예 1-58Synthesis Example 1-58
화합물 AC(15 g, 50.8 mmol)와 화합물 Trz40(23.7 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-58을 19.3 g 제조하였다.(수율 66%, MS: [M+H]+= 577)Compound AC (15 g, 50.8 mmol) and compound Trz40 (23.7 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.3 g of compound 1-58. (Yield 66%, MS: [M+H] + = 577)
합성예 1-59Synthesis Example 1-59
화합물 AC(15 g, 50.8 mmol)와 화합물 Trz41(28.5 g, 53.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(21.1 g, 152.5 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.5 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-59를 24.7 g 제조하였다.(수율 73%, MS: [M+H]+= 667)Compound AC (15 g, 50.8 mmol) and compound Trz41 (28.5 g, 53.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.7 g of Compound 1-59. (Yield 73%, MS: [M+H] + = 667)
합성예 2-1Synthesis Example 2-1
질소 분위기에서 화합물 2-AA(10 g, 35.8 mmol), 화합물 amine1(16 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-1 16.8 g을 얻었다.(수율 68%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-AA (10 g, 35.8 mmol), compound amine1 (16 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.8 g of Compound 2-1. (Yield 68%, MS: [M+H] + = 691)
합성예 2-2Synthesis Example 2-2
질소 분위기에서 화합물 2-AB(10 g, 35.8 mmol), 화합물 amine2(12.9 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-2 13.2 g을 얻었다.(수율 61%, MS: [M+H]+= 605)In a nitrogen atmosphere, compound 2-AB (10 g, 35.8 mmol), compound amine2 (12.9 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of Compound 2-2. (Yield 61%, MS: [M+H] + = 605)
합성예 2-3Synthesis Example 2-3
질소 분위기에서 화합물 2-AC(10 g, 35.8 mmol), 화합물 amine3(16 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-3 17.3 g을 얻었다.(수율 70%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-AC (10 g, 35.8 mmol), compound amine3 (16 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.3 g of compound 2-3. (Yield 70%, MS: [M+H] + = 691)
합성예 2-4Synthesis Example 2-4
질소 분위기에서 화합물 2-AD(10 g, 35.8 mmol), 화합물 amine4(10.6 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-4 12.7 g을 얻었다.(수율 66%, MS: [M+H]+= 539)In a nitrogen atmosphere, compound 2-AD (10 g, 35.8 mmol), compound amine4 (10.6 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of Compound 2-4. (Yield 66%, MS: [M+H] + = 539)
합성예 2-5Synthesis Example 2-5
질소 분위기에서 화합물 2-AE(10 g, 35.8 mmol), 화합물 amine5(13.3 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-5 13.4 g을 얻었다.(수율 61%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-AE (10 g, 35.8 mmol), compound amine5 (13.3 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of Compound 2-5. (Yield 61%, MS: [M+H] + = 615)
합성예 2-6Synthesis Example 2-6
질소 분위기에서 화합물 2-AE(10 g, 35.8 mmol), 화합물 amine6(12 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-6 13.4 g을 얻었다.(수율 65%, MS: [M+H]+= 579)In a nitrogen atmosphere, compound 2-AE (10 g, 35.8 mmol), compound amine6 (12 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 2-6. (Yield 65%, MS: [M+H] + = 579)
합성예 2-7Synthesis Example 2-7
질소 분위기에서 화합물 2-AF(10 g, 35.8 mmol), 화합물 amine7(12.3 g, 35.8 mmol), sodium tert-butoxide(11.4 g, 53.6 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-7 13.5 g을 얻었다.(수율 64%, MS: [M+H]+= 589)In a nitrogen atmosphere, compound 2-AF (10 g, 35.8 mmol), compound amine7 (12.3 g, 35.8 mmol), and sodium tert-butoxide (11.4 g, 53.6 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound 2-7. (Yield 64%, MS: [M+H] + = 589)
합성예 2-8Synthesis Example 2-8
질소 분위기에서 화합물 2-AA(15 g, 53.6 mmol)와 화합물 amine8(25.6 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-8을 23.9 g 제조하였다.(수율 68%, MS: [M+H]+= 655)In a nitrogen atmosphere, compound 2-AA (15 g, 53.6 mmol) and compound amine8 (25.6 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.9 g of Compound 2-8. (Yield 68%, MS: [M+H] + = 655)
합성예 2-9Synthesis Example 2-9
질소 분위기에서 화합물 2-AB(15 g, 53.6 mmol)와 화합물 amine9(29.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-9를 23.9 g 제조하였다.(수율 61%, MS: [M+H]+= 730)In a nitrogen atmosphere, compound 2-AB (15 g, 53.6 mmol) and compound amine9 (29.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.9 g of compound 2-9. (Yield 61%, MS: [M+H] + = 730)
합성예 2-10Synthesis Example 2-10
질소 분위기에서 화합물 2-AC(15 g, 53.6 mmol)와 화합물 amine10(29.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-10을 24.2 g 제조하였다.(수율 62%, MS: [M+H]+= 730)In a nitrogen atmosphere, compound 2-AC (15 g, 53.6 mmol) and compound amine10 (29.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of Compound 2-10. (Yield 62%, MS: [M+H] + = 730)
합성예 2-11Synthesis Example 2-11
질소 분위기에서 화합물 2-AD(15 g, 53.6 mmol)와 화합물 amine11(24.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-11을 20.9 g 제조하였다.(수율 61%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-AD (15 g, 53.6 mmol) and compound amine11 (24.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.9 g of Compound 2-11. (Yield 61%, MS: [M+H] + = 641)
합성예 2-12Synthesis Example 2-12
질소 분위기에서 화합물 2-AD(15 g, 53.6 mmol)와 화합물 amine12(30.5 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-12를 25.8 g 제조하였다.(수율 65%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-AD (15 g, 53.6 mmol) and compound amine12 (30.5 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.8 g of compound 2-12. (Yield 65%, MS: [M+H] + = 741)
합성예 2-13Synthesis Example 2-13
질소 분위기에서 화합물 2-AE(15 g, 53.6 mmol)와 화합물 amine13(21.4 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-13을 18.6 g 제조하였다.(수율 60%, MS: [M+H]+= 579)In a nitrogen atmosphere, compound 2-AE (15 g, 53.6 mmol) and compound amine13 (21.4 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.6 g of Compound 2-13. (Yield 60%, MS: [M+H] + = 579)
합성예 2-14Synthesis Example 2-14
질소 분위기에서 화합물 2-AE(15 g, 53.6 mmol)와 화합물 amine14(23.4 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-14를 22.1 g 제조하였다.(수율 67%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-AE (15 g, 53.6 mmol) and compound amine14 (23.4 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.1 g of compound 2-14. (Yield 67%, MS: [M+H] + = 615)
합성예 2-15Synthesis Example 2-15
질소 분위기에서 화합물 2-AE(15 g, 53.6 mmol)와 화합물 amine15(29.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-15를 24.2 g 제조하였다.(수율 62%, MS: [M+H]+= 730)In a nitrogen atmosphere, compound 2-AE (15 g, 53.6 mmol) and compound amine15 (29.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.2 g of Compound 2-15. (Yield 62%, MS: [M+H] + = 730)
합성예 2-16Synthesis Example 2-16
질소 분위기에서 화합물 2-AE(15 g, 53.6 mmol)와 화합물 amine11(24.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-16을 23 g 제조하였다.(수율 67%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-AE (15 g, 53.6 mmol) and compound amine11 (24.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23 g of compound 2-16. (Yield 67%, MS: [M+H] + = 641)
합성예 2-17Synthesis Example 2-17
질소 분위기에서 화합물 2-AF(15 g, 53.6 mmol)와 화합물 amine16(27.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-17을 23.5 g 제조하였다.(수율 63%, MS: [M+H]+= 695)In a nitrogen atmosphere, compound 2-AF (15 g, 53.6 mmol) and compound amine16 (27.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.5 g of Compound 2-17. (Yield 63%, MS: [M+H] + = 695)
합성예 2-18Synthesis Example 2-18
질소 분위기에서 화합물 2-AA(15 g, 53.6 mmol)와 화합물 amine17(36.2 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-18을 28.5 g 제조하였다.(수율 63%, MS: [M+H]+= 843)In a nitrogen atmosphere, compound 2-AA (15 g, 53.6 mmol) and compound amine17 (36.2 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.5 g of Compound 2-18. (Yield 63%, MS: [M+H] + = 843)
합성예 2-19Synthesis Example 2-19
질소 분위기에서 화합물 2-AD(15 g, 53.6 mmol)와 화합물 amine18(24.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-19를 23.3 g 제조하였다.(수율 68%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-AD (15 g, 53.6 mmol) and compound amine18 (24.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.3 g of compound 2-19. (Yield 68%, MS: [M+H] + = 641)
합성예 2-20Synthesis Example 2-20
질소 분위기에서 화합물 2-AF(15 g, 53.6 mmol)와 화합물 amine19(34.8 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-20을 27.6 g 제조하였다.(수율 63%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-AF (15 g, 53.6 mmol) and compound amine19 (34.8 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.6 g of compound 2-20. (Yield 63%, MS: [M+H] + = 817)
합성예 2-21Synthesis Example 2-21
질소 분위기에서 화합물 2-AA(15 g, 53.6 mmol)와 화합물 amine20(33.3 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-21을 27.5 g 제조하였다.(수율 65%, MS: [M+H]+= 791)In a nitrogen atmosphere, compound 2-AA (15 g, 53.6 mmol) and compound amine20 (33.3 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.5 g of Compound 2-21. (Yield 65%, MS: [M+H] + = 791)
합성예 2-22Synthesis Example 2-22
질소 분위기에서 화합물 2-AD(15 g, 53.6 mmol)와 화합물 amine21(32 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-22를 27.9 g 제조하였다.(수율 68%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-AD (15 g, 53.6 mmol) and compound amine21 (32 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.9 g of compound 2-22. (Yield 68%, MS: [M+H] + = 767)
합성예 2-23Synthesis Example 2-23
질소 분위기에서 화합물 2-AE(15 g, 53.6 mmol)와 화합물 amine22(23.4 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-23을 22.4 g 제조하였다.(수율 68%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-AE (15 g, 53.6 mmol) and compound amine22 (23.4 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound 2-23. (Yield 68%, MS: [M+H] + = 615)
합성예 2-24Synthesis Example 2-24
질소 분위기에서 화합물 2-AH(10 g, 28.1 mmol), 화합물 amine23(11.2 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-24 14.1 g을 얻었다.(수율 70%, MS: [M+H]+= 717)In a nitrogen atmosphere, compound 2-AH (10 g, 28.1 mmol), compound amine23 (11.2 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of compound 2-24. (Yield 70%, MS: [M+H] + = 717)
합성예 2-25Synthesis Example 2-25
질소 분위기에서 화합물 2-AJ(10 g, 28.1 mmol), 화합물 amine24(12.6 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-25 13.1 g을 얻었다.(수율 61%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-AJ (10 g, 28.1 mmol), compound amine24 (12.6 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-25. (Yield 61%, MS: [M+H] + = 767)
합성예 2-26Synthesis Example 2-26
질소 분위기에서 화합물 2-AJ(10 g, 28.1 mmol), 화합물 amine25(10.4 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-26 11.8 g을 얻었다.(수율 61%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-AJ (10 g, 28.1 mmol), compound amine25 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-26. (Yield 61%, MS: [M+H] + = 691)
합성예 2-27Synthesis Example 2-27
질소 분위기에서 화합물 2-AK(10 g, 28.1 mmol), 화합물 amine26(9.8 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-27 11.6 g을 얻었다.(수율 62%, MS: [M+H]+= 669)In a nitrogen atmosphere, compound 2-AK (10 g, 28.1 mmol), compound amine26 (9.8 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 2-27. (Yield 62%, MS: [M+H] + = 669)
합성예 2-28Synthesis Example 2-28
질소 분위기에서 화합물 2-AK(15 g, 42.2 mmol)와 화합물 amine27(16.2 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-28을 16.2 g 제조하였다.(수율 60%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-AK (15 g, 42.2 mmol) and compound amine27 (16.2 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound 2-28. (Yield 60%, MS: [M+H] + = 641)
합성예 2-29Synthesis Example 2-29
질소 분위기에서 화합물 2-AI(15 g, 42.2 mmol)와 화합물 amine28(19.5 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-29를 18.1 g 제조하였다.(수율 60%, MS: [M+H]+= 717)In a nitrogen atmosphere, compound 2-AI (15 g, 42.2 mmol) and compound amine28 (19.5 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.1 g of Compound 2-29. (Yield 60%, MS: [M+H] + = 717)
합성예 2-30Synthesis Example 2-30
질소 분위기에서 화합물 2-AG(15 g, 42.2 mmol)와 화합물 amine29(25.1 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-30을 22.7 g 제조하였다.(수율 64%, MS: [M+H]+= 843)In a nitrogen atmosphere, compound 2-AG (15 g, 42.2 mmol) and compound amine29 (25.1 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of Compound 2-30. (Yield 64%, MS: [M+H] + = 843)
합성예 2-31Synthesis Example 2-31
질소 분위기에서 화합물 2-AJ(15 g, 42.2 mmol)와 화합물 amine30(22.9 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-31을 22.4 g 제조하였다.(수율 67%, MS: [M+H]+= 793)In a nitrogen atmosphere, compound 2-AJ (15 g, 42.2 mmol) and compound amine30 (22.9 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.4 g of compound 2-31. (Yield 67%, MS: [M+H] + = 793)
합성예 2-32Synthesis Example 2-32
질소 분위기에서 화합물 2-AI(15 g, 42.2 mmol)와 화합물 amine31(21.8 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-32를 22.6 g 제조하였다.(수율 70%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-AI (15 g, 42.2 mmol) and compound amine31 (21.8 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.6 g of compound 2-32. (Yield 70%, MS: [M+H] + = 767)
합성예 2-33Synthesis Example 2-33
질소 분위기에서 화합물 2-AL(15 g, 42.2 mmol)와 화합물 amine32(22.9 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-33을 23.4 g 제조하였다.(수율 70%, MS: [M+H]+= 793)In a nitrogen atmosphere, compound 2-AL (15 g, 42.2 mmol) and compound amine32 (22.9 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.4 g of compound 2-33. (Yield 70%, MS: [M+H] + = 793)
합성예 2-34Synthesis Example 2-34
질소 분위기에서 화합물 2-AK(15 g, 42.2 mmol)와 화합물 amine33(25.1 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-34를 21.3 g 제조하였다.(수율 60%, MS: [M+H]+= 843)In a nitrogen atmosphere, compound 2-AK (15 g, 42.2 mmol) and compound amine33 (25.1 g, 44.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.3 g of compound 2-34. (Yield 60%, MS: [M+H] + = 843)
합성예 2-35Synthesis Example 2-35
질소 분위기에서 화합물 2-AI(15 g, 42.2 mmol)와 화합물 amine34(22.4 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-35를 22.7 g 제조하였다.(수율 69%, MS: [M+H]+= 781)In a nitrogen atmosphere, compound 2-AI (15 g, 42.2 mmol) and compound amine34 (22.4 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of compound 2-35. (Yield 69%, MS: [M+H] + = 781)
합성예 2-36Synthesis Example 2-36
질소 분위기에서 화합물 2-AH(15 g, 42.2 mmol)와 화합물 amine35(22.8 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-36을 23 g 제조하였다.(수율 69%, MS: [M+H]+= 791)In a nitrogen atmosphere, compound 2-AH (15 g, 42.2 mmol) and compound amine35 (22.8 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23 g of compound 2-36. (Yield 69%, MS: [M+H] + = 791)
합성예 2-37Synthesis Example 2-37
질소 분위기에서 화합물 2-AQ(10 g, 30.3 mmol), 화합물 amine36(11.1 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-37 13.6 g을 얻었다.(수율 68%, MS: [M+H]+= 659)In a nitrogen atmosphere, compound 2-AQ (10 g, 30.3 mmol), compound amine36 (11.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 2-37. (Yield 68%, MS: [M+H] + = 659)
합성예 2-38Synthesis Example 2-38
질소 분위기에서 화합물 2-AO(10 g, 30.3 mmol), 화합물 amine37(13.6 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-38 14.4 g을 얻었다.(수율 64%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-AO (10 g, 30.3 mmol), compound amine37 (13.6 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.4 g of compound 2-38. (Yield 64%, MS: [M+H] + = 741)
합성예 2-39Synthesis Example 2-39
질소 분위기에서 화합물 2-AQ(10 g, 30.3 mmol), 화합물 amine38(10.2 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-39 12 g을 얻었다.(수율 63%, MS: [M+H]+= 629)In a nitrogen atmosphere, compound 2-AQ (10 g, 30.3 mmol), compound amine38 (10.2 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12 g of compound 2-39. (Yield 63%, MS: [M+H] + = 629)
합성예 2-40Synthesis Example 2-40
질소 분위기에서 화합물 2-AQ(15 g, 45.5 mmol)와 화합물 amine27(17.4 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-40을 18.4 g 제조하였다.(수율 66%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-AQ (15 g, 45.5 mmol) and compound amine27 (17.4 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.4 g of Compound 2-40. (Yield 66%, MS: [M+H] + = 615)
합성예 2-41Synthesis Example 2-41
질소 분위기에서 화합물 2-AN(15 g, 45.5 mmol)와 화합물 amine39(24.7 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-41을 20.9 g 제조하였다.(수율 60%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-AN (15 g, 45.5 mmol) and compound amine39 (24.7 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.9 g of Compound 2-41. (Yield 60%, MS: [M+H] + = 767)
합성예 2-42Synthesis Example 2-42
질소 분위기에서 화합물 2-AR(15 g, 45.5 mmol)와 화합물 amine40(21.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-42를 20.7 g 제조하였다.(수율 66%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-AR (15 g, 45.5 mmol) and compound amine40 (21.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.7 g of compound 2-42. (Yield 66%, MS: [M+H] + = 691)
합성예 2-43Synthesis Example 2-43
질소 분위기에서 화합물 2-AP(15 g, 45.5 mmol)와 화합물 amine41(27.8 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-43을 26.1 g 제조하였다.(수율 69%, MS: [M+H]+= 831)In a nitrogen atmosphere, compound 2-AP (15 g, 45.5 mmol) and compound amine41 (27.8 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.1 g of compound 2-43. (Yield 69%, MS: [M+H] + = 831)
합성예 2-44Synthesis Example 2-44
질소 분위기에서 화합물 2-AQ(15 g, 45.5 mmol)와 화합물 amine42(23.5 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-44를 22.9 g 제조하였다.(수율 68%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-AQ (15 g, 45.5 mmol) and compound amine42 (23.5 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.9 g of compound 2-44. (Yield 68%, MS: [M+H] + = 741)
합성예 2-45Synthesis Example 2-45
질소 분위기에서 화합물 2-AN(15 g, 45.5 mmol)와 화합물 amine43(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-45를 26 g 제조하였다.(수율 70%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-AN (15 g, 45.5 mmol) and compound amine43 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 2-45. (Yield 70%, MS: [M+H] + = 817)
합성예 2-46Synthesis Example 2-46
질소 분위기에서 화합물 2-AQ(15 g, 45.5 mmol)와 화합물 amine44(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-46을 22.3 g 제조하였다.(수율 60%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-AQ (15 g, 45.5 mmol) and compound amine44 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.3 g of compound 2-46. (Yield 60%, MS: [M+H] + = 817)
합성예 2-47Synthesis Example 2-47
질소 분위기에서 화합물 2-AO (15 g, 43.4 mmol)와 화합물 amine45(25.8 g, 45.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18 g, 130.1 mmol)를 물 54 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-47을 19.5 g 제조하였다.(수율 54%, MS: [M+H]+= 833)In a nitrogen atmosphere, compound 2-AO (15 g, 43.4 mmol) and compound amine45 (25.8 g, 45.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in 54 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.5 g of compound 2-47. (Yield 54%, MS: [M+H] + = 833)
합성예 2-48Synthesis Example 2-48
질소 분위기에서 화합물 2-AP(15 g, 45.5 mmol)와 화합물 amine46(23.5 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-48을 20.2 g 제조하였다.(수율 60%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-AP (15 g, 45.5 mmol) and compound amine46 (23.5 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of compound 2-48. (Yield 60%, MS: [M+H] + = 741)
합성예 2-49Synthesis Example 2-49
질소 분위기에서 화합물 2-AN(15 g, 45.5 mmol)와 화합물 amine47(23.5 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-49를 21.5 g 제조하였다.(수율 64%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-AN (15 g, 45.5 mmol) and compound amine47 (23.5 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.5 g of compound 2-49. (Yield 64%, MS: [M+H] + = 741)
합성예 2-50Synthesis Example 2-50
질소 분위기에서 화합물 2-BA(10 g, 30.3 mmol), 화합물 amine48(12.1 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-50 11.8 g을 얻었다.(수율 61%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-BA (10 g, 30.3 mmol), compound amine48 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-50. (Yield 61%, MS: [M+H] + = 641)
합성예 2-51Synthesis Example 2-51
질소 분위기에서 화합물 2-BA(10 g, 30.3 mmol), 화합물 amine49(11.3 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-51 11.7 g을 얻었다.(수율 63%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-BA (10 g, 30.3 mmol), compound amine49 (11.3 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of compound 2-51. (Yield 63%, MS: [M+H] + = 615)
합성예 2-52Synthesis Example 2-52
질소 분위기에서 화합물 2-BB(10 g, 30.3 mmol), 화합물 amine50(12.9 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-52 14 g을 얻었다.(수율 69%, MS: [M+H]+= 668)In a nitrogen atmosphere, compound 2-BB (10 g, 30.3 mmol), compound amine50 (12.9 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14 g of compound 2-52. (Yield 69%, MS: [M+H] + = 668)
합성예 2-53Synthesis Example 2-53
질소 분위기에서 화합물 2-BC(10 g, 30.3 mmol), 화합물 amine51(14 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-53 12.8 g을 얻었다.(수율 60%, MS: [M+H]+= 704)In a nitrogen atmosphere, compound 2-BC (10 g, 30.3 mmol), compound amine51 (14 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 2-53. (Yield 60%, MS: [M+H] + = 704)
합성예 2-54Synthesis Example 2-54
질소 분위기에서 화합물 2-BD(10 g, 30.3 mmol), 화합물 amine52(13.6 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-54 12.6 g을 얻었다.(수율 60%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BD (10 g, 30.3 mmol), compound amine52 (13.6 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound 2-54. (Yield 60%, MS: [M+H] + = 691)
합성예 2-55Synthesis Example 2-55
질소 분위기에서 화합물 2-BE(10 g, 30.3 mmol), 화합물 amine53(12.1 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-55 13.2 g을 얻었다.(수율 68%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-BE (10 g, 30.3 mmol), compound amine53 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound 2-55. (Yield 68%, MS: [M+H] + = 641)
합성예 2-56Synthesis Example 2-56
질소 분위기에서 화합물 2-BA(15 g, 53.6 mmol)와 화합물 amine54(27.1 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-56을 21.9 g 제조하였다.(수율 60%, MS: [M+H]+= 681)In a nitrogen atmosphere, compound 2-BA (15 g, 53.6 mmol) and compound amine54 (27.1 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.9 g of compound 2-56. (Yield 60%, MS: [M+H] + = 681)
합성예 2-57Synthesis Example 2-57
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine55(26.5 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-57을 23 g 제조하였다.(수율 64%, MS: [M+H]+= 671)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine55 (26.5 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23 g of compound 2-57. (Yield 64%, MS: [M+H] + = 671)
합성예 2-58Synthesis Example 2-58
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine56(24.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-58을 22.7 g 제조하였다.(수율 66%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine56 (24.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of compound 2-58. (Yield 66%, MS: [M+H] + = 641)
합성예 2-59Synthesis Example 2-59
질소 분위기에서 화합물 2-BE(15 g, 53.6 mmol)와 화합물 amine57(22.3 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-59를 22.3 g 제조하였다.(수율 70%, MS: [M+H]+= 595)In a nitrogen atmosphere, compound 2-BE (15 g, 53.6 mmol) and compound amine57 (22.3 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.3 g of compound 2-59. (Yield 70%, MS: [M+H] + = 595)
합성예 2-60Synthesis Example 2-60
질소 분위기에서 화합물 2-BF(15 g, 53.6 mmol)와 화합물 amine58(32.7 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-60을 25.5 g 제조하였다.(수율 61%, MS: [M+H]+= 780)In a nitrogen atmosphere, compound 2-BF (15 g, 53.6 mmol) and compound amine58 (32.7 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound 2-60. (Yield 61%, MS: [M+H] + = 780)
합성예 2-61Synthesis Example 2-61
질소 분위기에서 화합물 2-BE(15 g, 53.6 mmol)와 화합물 amine59(36.2 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-61을 31.6 g 제조하였다.(수율 70%, MS: [M+H]+= 843)In a nitrogen atmosphere, compound 2-BE (15 g, 53.6 mmol) and compound amine59 (36.2 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 31.6 g of compound 2-61. (Yield 70%, MS: [M+H] + = 843)
합성예 2-62Synthesis Example 2-62
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine60(29.9 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-62를 26.2 g 제조하였다.(수율 67%, MS: [M+H]+= 730)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine60 (29.9 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.2 g of compound 2-62. (Yield 67%, MS: [M+H] + = 730)
합성예 2-63Synthesis Example 2-63
질소 분위기에서 화합물 2-BD(15 g, 53.6 mmol)와 화합물 amine61(27.7 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-63을 22.2 g 제조하였다.(수율 60%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BD (15 g, 53.6 mmol) and compound amine61 (27.7 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.2 g of compound 2-63. (Yield 60%, MS: [M+H] + = 691)
합성예 2-64Synthesis Example 2-64
질소 분위기에서 화합물 2-BE(15 g, 53.6 mmol)와 화합물 amine62(23.4 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-64를 21.1 g 제조하였다.(수율 64%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-BE (15 g, 53.6 mmol) and compound amine62 (23.4 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.1 g of compound 2-64. (Yield 64%, MS: [M+H] + = 615)
합성예 2-65Synthesis Example 2-65
질소 분위기에서 화합물 2-BD(15 g, 53.6 mmol)와 화합물 amine63(22.8 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-65를 21.7 g 제조하였다.(수율 67%, MS: [M+H]+= 605)In a nitrogen atmosphere, compound 2-BD (15 g, 53.6 mmol) and compound amine63 (22.8 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.7 g of compound 2-65. (Yield 67%, MS: [M+H] + = 605)
합성예 2-66Synthesis Example 2-66
질소 분위기에서 화합물 2-BF(15 g, 53.6 mmol)와 화합물 amine64(31.6 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-66을 26.9 g 제조하였다.(수율 66%, MS: [M+H]+= 760)In a nitrogen atmosphere, compound 2-BF (15 g, 53.6 mmol) and compound amine64 (31.6 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.9 g of compound 2-66. (Yield 66%, MS: [M+H] + = 760)
합성예 2-67Synthesis Example 2-67
질소 분위기에서 화합물 2-BB(15 g, 53.6 mmol)와 화합물 amine65(32 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-67을 27.1 g 제조하였다.(수율 66%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-BB (15 g, 53.6 mmol) and compound amine65 (32 g, 56.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.1 g of compound 2-67. (Yield 66%, MS: [M+H] + = 767)
합성예 2-68Synthesis Example 2-68
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine66(32 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-68을 19.8 g 제조하였다.(수율 65%, MS: [M+H]+= 569)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine66 (32 g, 56.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.8 g of compound 2-68. (Yield 65%, MS: [M+H] + = 569)
합성예 2-69Synthesis Example 2-69
질소 분위기에서 화합물 2-BB(15 g, 53.6 mmol)와 화합물 amine67(29.1 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-69를 26.5 g 제조하였다.(수율 69%, MS: [M+H]+= 717)In a nitrogen atmosphere, compound 2-BB (15 g, 53.6 mmol) and compound amine67 (29.1 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.5 g of compound 2-69. (Yield 69%, MS: [M+H] + = 717)
합성예 2-70Synthesis Example 2-70
질소 분위기에서 화합물 2-BF(15 g, 53.6 mmol)와 화합물 amine68(30.5 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-70을 25 g 제조하였다.(수율 63%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-BF (15 g, 53.6 mmol) and compound amine68 (30.5 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25 g of compound 2-70. (Yield 63%, MS: [M+H] + = 741)
합성예 2-71Synthesis Example 2-71
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine69(26.2 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-71을 22.1 g 제조하였다.(수율 62%, MS: [M+H]+= 665)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine69 (26.2 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.1 g of Compound 2-71. (Yield 62%, MS: [M+H] + = 665)
합성예 2-72Synthesis Example 2-72
질소 분위기에서 화합물 2-BF(15 g, 53.6 mmol)와 화합물 amine70(23.4 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-72를 21.7 g 제조하였다.(수율 66%, MS: [M+H]+= 615)In a nitrogen atmosphere, compound 2-BF (15 g, 53.6 mmol) and compound amine70 (23.4 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.7 g of compound 2-72. (Yield 66%, MS: [M+H] + = 615)
합성예 2-73Synthesis Example 2-73
질소 분위기에서 화합물 2-BE(15 g, 53.6 mmol)와 화합물 amine71(32 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-73을 25.5 g 제조하였다.(수율 62%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-BE (15 g, 53.6 mmol) and compound amine71 (32 g, 56.3 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound 2-73. (Yield 62%, MS: [M+H] + = 767)
합성예 2-74Synthesis Example 2-74
질소 분위기에서 화합물 2-BD(15 g, 53.6 mmol)와 화합물 amine72(36.2 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-74를 30.7 g 제조하였다.(수율 68%, MS: [M+H]+= 843)In a nitrogen atmosphere, compound 2-BD (15 g, 53.6 mmol) and compound amine72 (36.2 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.7 g of Compound 2-74. (Yield 68%, MS: [M+H] + = 843)
합성예 2-75Synthesis Example 2-75
질소 분위기에서 화합물 2-BC(15 g, 53.6 mmol)와 화합물 amine73(39.1 g, 56.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(22.2 g, 160.9 mmol)를 물 67 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.6 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-75를 29.7 g 제조하였다.(수율 62%, MS: [M+H]+= 893)In a nitrogen atmosphere, compound 2-BC (15 g, 53.6 mmol) and compound amine73 (39.1 g, 56.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.2 g, 160.9 mmol) was dissolved in 67 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.7 g of Compound 2-75. (Yield 62%, MS: [M+H] + = 893)
합성예 2-76Synthesis Example 2-76
질소 분위기에서 화합물 2-BG(10 g, 28.1 mmol), 화합물 amine74(10.4 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-76 12.6 g을 얻었다.(수율 65%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BG (10 g, 28.1 mmol), compound amine74 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound 2-76. (Yield 65%, MS: [M+H] + = 691)
합성예 2-77Synthesis Example 2-77
질소 분위기에서 화합물 2-BI(10 g, 28.1 mmol), 화합물 amine75(9.4 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-77 11 g을 얻었다.(수율 60%, MS: [M+H]+= 655)In a nitrogen atmosphere, compound 2-BI (10 g, 28.1 mmol), compound amine75 (9.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11 g of compound 2-77. (Yield 60%, MS: [M+H] + = 655)
합성예 2-78Synthesis Example 2-78
질소 분위기에서 화합물 2-BJ(10 g, 28.1 mmol), 화합물 amine76(10.4 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-78 11.8 g을 얻었다.(수율 61%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BJ (10 g, 28.1 mmol), compound amine76 (10.4 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-78. (Yield 61%, MS: [M+H] + = 691)
합성예 2-79Synthesis Example 2-79
질소 분위기에서 화합물 2-BK(10 g, 28.1 mmol), 화합물 amine77(11.8 g, 28.1 mmol), sodium tert-butoxide(8.9 g, 42.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-79 13.1 g을 얻었다.(수율 63%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-BK (10 g, 28.1 mmol), compound amine77 (11.8 g, 28.1 mmol), and sodium tert-butoxide (8.9 g, 42.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-79. (Yield 63%, MS: [M+H] + = 741)
합성예 2-80Synthesis Example 2-80
질소 분위기에서 화합물 2-BJ(15 g, 42.2 mmol)와 화합물 amine78(16.2 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-80을 18.1 g 제조하였다.(수율 67%, MS: [M+H]+= 641)In a nitrogen atmosphere, compound 2-BJ (15 g, 42.2 mmol) and compound amine78 (16.2 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.1 g of Compound 2-80. (Yield 67%, MS: [M+H] + = 641)
합성예 2-81Synthesis Example 2-81
질소 분위기에서 화합물 2-BG(15 g, 42.2 mmol)와 화합물 amine79(21.8 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-81을 19.7 g 제조하였다.(수율 61%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-BG (15 g, 42.2 mmol) and compound amine79 (21.8 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of compound 2-81. (Yield 61%, MS: [M+H] + = 767)
합성예 2-82Synthesis Example 2-82
질소 분위기에서 화합물 2-BI(15 g, 42.2 mmol)와 화합물 amine80(26.3 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-82를 24.9 g 제조하였다.(수율 68%, MS: [M+H]+= 869)In a nitrogen atmosphere, compound 2-BI (15 g, 42.2 mmol) and compound amine80 (26.3 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.9 g of compound 2-82. (Yield 68%, MS: [M+H] + = 869)
합성예 2-83Synthesis Example 2-83
질소 분위기에서 화합물 2-BH(15 g, 42.2 mmol)와 화합물 amine81(20.2 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-83을 19.7 g 제조하였다.(수율 64%, MS: [M+H]+= 731)In a nitrogen atmosphere, compound 2-BH (15 g, 42.2 mmol) and compound amine81 (20.2 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of compound 2-83. (Yield 64%, MS: [M+H] + = 731)
합성예 2-84Synthesis Example 2-84
질소 분위기에서 화합물 2-BG(15 g, 42.2 mmol)와 화합물 amine82(21.8 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-84를 20 g 제조하였다.(수율 62%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-BG (15 g, 42.2 mmol) and compound amine82 (21.8 g, 44.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20 g of compound 2-84. (Yield 62%, MS: [M+H] + = 767)
합성예 2-85Synthesis Example 2-85
질소 분위기에서 화합물 2-BL(15 g, 42.2 mmol)와 화합물 amine83(22.9 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-85를 20 g 제조하였다.(수율 60%, MS: [M+H]+= 793)In a nitrogen atmosphere, compound 2-BL (15 g, 42.2 mmol) and compound amine83 (22.9 g, 44.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of compound 2-85. (Yield 60%, MS: [M+H] + = 793)
합성예 2-86Synthesis Example 2-86
질소 분위기에서 화합물 2-BG(15 g, 42.2 mmol)와 화합물 amine84(23.5 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-86을 23.5 g 제조하였다.(수율 69%, MS: [M+H]+= 807)In a nitrogen atmosphere, compound 2-BG (15 g, 42.2 mmol) and compound amine84 (23.5 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.5 g of compound 2-86. (Yield 69%, MS: [M+H] + = 807)
합성예 2-87Synthesis Example 2-87
질소 분위기에서 화합물 2-BI(15 g, 42.2 mmol)와 화합물 amine85(22.4 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-87을 22.7 g 제조하였다.(수율 69%, MS: [M+H]+= 781)In a nitrogen atmosphere, compound 2-BI (15 g, 42.2 mmol) and compound amine85 (22.4 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of compound 2-87. (Yield 69%, MS: [M+H] + = 781)
합성예 2-88Synthesis Example 2-88
질소 분위기에서 화합물 2-BJ(15 g, 42.2 mmol)와 화합물 amine86(20.6 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-88을 20.6 g 제조하였다.(수율 66%, MS: [M+H]+= 741)In a nitrogen atmosphere, compound 2-BJ (15 g, 42.2 mmol) and compound amine86 (20.6 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.6 g of compound 2-88. (Yield 66%, MS: [M+H] + = 741)
합성예 2-89Synthesis Example 2-89
질소 분위기에서 화합물 2-BI(15 g, 42.2 mmol)와 화합물 amine87(22.4 g, 44.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.5 g, 126.5 mmol)를 물 52 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.4 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-89를 20.4 g 제조하였다.(수율 62%, MS: [M+H]+= 781)In a nitrogen atmosphere, compound 2-BI (15 g, 42.2 mmol) and compound amine87 (22.4 g, 44.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.5 g, 126.5 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound 2-89. (Yield 62%, MS: [M+H] + = 781)
합성예 2-90Synthesis Example 2-90
질소 분위기에서 화합물 2-BN(10 g, 30.3 mmol), 화합물 amine88(11.3 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-90 13.3 g을 얻었다.(수율 66%, MS: [M+H]+= 665)In a nitrogen atmosphere, compound 2-BN (10 g, 30.3 mmol), compound amine88 (11.3 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound 2-90. (Yield 66%, MS: [M+H] + = 665)
합성예 2-91Synthesis Example 2-91
질소 분위기에서 화합물 2-BM(10 g, 30.3 mmol), 화합물 amine89(12.8 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 2 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-91 13.4 g을 얻었다.(수율 62%, MS: [M+H]+= 715)In a nitrogen atmosphere, compound 2-BM (10 g, 30.3 mmol), compound amine89 (12.8 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 2-91. (Yield 62%, MS: [M+H] + = 715)
합성예 2-92Synthesis Example 2-92
질소 분위기에서 화합물 2-BP(10 g, 30.3 mmol), 화합물 amine90(12.1 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-92 13.8 g을 얻었다.(수율 66%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BP (10 g, 30.3 mmol), compound amine90 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound 2-92. (Yield 66%, MS: [M+H] + = 691)
합성예 2-93Synthesis Example 2-93
질소 분위기에서 화합물 2-BQ(10 g, 30.3 mmol), 화합물 amine91(12.1 g, 30.3 mmol), sodium tert-butoxide(9.7 g, 45.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol)을 투입했다. 3 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-93 13.4 g을 얻었다.(수율 64%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BQ (10 g, 30.3 mmol), compound amine91 (12.1 g, 30.3 mmol), and sodium tert-butoxide (9.7 g, 45.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 2-93. (Yield 64%, MS: [M+H] + = 691)
합성예 2-94Synthesis Example 2-94
질소 분위기에서 화합물 2-BP(15 g, 45.5 mmol)와 화합물 amine92(25.6 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-94를 21.8 g 제조하였다.(수율 61%, MS: [M+H]+= 785)In a nitrogen atmosphere, compound 2-BP (15 g, 45.5 mmol) and compound amine92 (25.6 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.8 g of compound 2-94. (Yield 61%, MS: [M+H] + = 785)
합성예 2-95Synthesis Example 2-95
질소 분위기에서 화합물 2-BN(15 g, 45.5 mmol)와 화합물 amine93(26 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-95를 24.6 g 제조하였다.(수율 68%, MS: [M+H]+= 795)In a nitrogen atmosphere, compound 2-BN (15 g, 45.5 mmol) and compound amine93 (26 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.6 g of Compound 2-95. (Yield 68%, MS: [M+H] + = 795)
합성예 2-96Synthesis Example 2-96
질소 분위기에서 화합물 2-BP(15 g, 45.5 mmol)와 화합물 amine94(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-96을 25.6 g 제조하였다.(수율 69%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-BP (15 g, 45.5 mmol) and compound amine94 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.6 g of compound 2-96. (Yield 69%, MS: [M+H] + = 817)
합성예 2-97Synthesis Example 2-97
질소 분위기에서 화합물 2-BN(15 g, 45.5 mmol)와 화합물 amine95(30.7 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-97을 25.2 g 제조하였다.(수율 62%, MS: [M+H]+= 893)In a nitrogen atmosphere, compound 2-BN (15 g, 45.5 mmol) and compound amine95 (30.7 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.2 g of Compound 2-97. (Yield 62%, MS: [M+H] + = 893)
합성예 2-98Synthesis Example 2-98
질소 분위기에서 화합물 2-BR(15 g, 45.5 mmol)와 화합물 amine96(21.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-98을 20.1 g 제조하였다.(수율 64%, MS: [M+H]+= 691)In a nitrogen atmosphere, compound 2-BR (15 g, 45.5 mmol) and compound amine96 (21.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.1 g of compound 2-98. (Yield 64%, MS: [M+H] + = 691)
합성예 2-99Synthesis Example 2-99
질소 분위기에 서 화합물 2-BP(15 g, 45.5 mmol)와 화합물 amine97(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-99를 23 g 제조하였다.(수율 62%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-BP (15 g, 45.5 mmol) and compound amine97 (27.1 g, 47.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23 g of compound 2-99. (Yield 62%, MS: [M+H] + = 817)
합성예 2-100Synthesis Example 2-100
질소 분위기에서 화합물 2-BN(15 g, 45.5 mmol)와 화합물 amine98(24.7 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-100을 22.3 g 제조하였다.(수율 64%, MS: [M+H]+= 767)In a nitrogen atmosphere, compound 2-BN (15 g, 45.5 mmol) and compound amine98 (24.7 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 2-100. (Yield 64%, MS: [M+H] + = 767)
합성예 2-101Synthesis Example 2-101
질소 분위기에서 화합물 2-BP(15 g, 45.5 mmol)와 화합물 amine99(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 101을 22.3 g 제조하였다.(수율 60%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-BP (15 g, 45.5 mmol) and compound amine99 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.3 g of Compound 101. (Yield 60%, MS: [M+H] + = 817)
합성예 2-102Synthesis Example 2-102
질소 분위기에서 화합물 2-BM(15 g, 45.5 mmol)와 화합물 amine100(25.9 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-102를 21.6 g 제조하였다.(수율 60%, MS: [M+H]+= 791)In a nitrogen atmosphere, compound 2-BM (15 g, 45.5 mmol) and compound amine100 (25.9 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.6 g of compound 2-102. (Yield 60%, MS: [M+H] + = 791)
합성예 2-103Synthesis Example 2-103
질소 분위기에서 화합물 2-BO(15 g, 45.5 mmol)와 화합물 amine101(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-103을 26 g 제조하였다.(수율 70%, MS: [M+H]+= 817)In a nitrogen atmosphere, compound 2-BO (15 g, 45.5 mmol) and compound amine101 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 2-103. (Yield 70%, MS: [M+H] + = 817)
합성예 2-104Synthesis Example 2-104
질소 분위기에서 화합물 2-BO(15 g, 45.5 mmol)와 화합물 amine102(24.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 10 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-104를 22.6 g 제조하였다.(수율 63%, MS: [M+H]+= 791)In a nitrogen atmosphere, compound 2-BO (15 g, 45.5 mmol) and compound amine102 (24.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.6 g of compound 2-104. (Yield 63%, MS: [M+H] + = 791)
합성예 2-105Synthesis Example 2-105
질소 분위기에서 화합물 2-BN(15 g, 45.5 mmol)와 화합물 amine103(27.1 g, 47.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.9 g, 136.5 mmol)를 물 57 ml에 녹여 투입하고 충분히 교반한 후 bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-105를 23.7 g 제조하였다.(수율 69%, MS: [M+H]+= 755)In a nitrogen atmosphere, compound 2-BN (15 g, 45.5 mmol) and compound amine103 (27.1 g, 47.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.5 mmol) was dissolved in 57 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.7 g of Compound 2-105. (Yield 69%, MS: [M+H] + = 755)
실시예 1Example 1
ITO(indium tin oxide)가 1000 Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척했다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용했다. ITO를 30 분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10 분간 진행했다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5 분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 하기 화합물 HI-1을 1150 Å의 두께로 형성하되 하기 화합물 A-1을 1.5 중량% 농도로 p-doping 했다. 상기 정공주입층 위에 하기 화합물 HT-1을 진공 증착하여 막 두께 800 Å의 정공수송층을 형성했다. 이어서, 상기 정공수송층 위에 막 두께 150 Å으로 하기 화합물 EB-1을 진공 증착하여 전자차단층을 형성했다. 이어서, 상기 EB-1 증착막 위에 하기 호스트로 화합물 1-1 과 화합물 2-1 및 도펀트로 하기 화합물 Dp-7을 49:49:2의 중량비로 진공 공증착하여 400 Å 두께의 적색 발광층을 형성했다. 상기 발광층 위에 막 두께 30 Å으로 하기 화합물 HB-1을 진공 증착하여 정공저지층을 형성했다. 이어서, 상기 정공저지층 위에 하기 화합물 ET-1과 하기 LiQ 화합물을 2:1의 중량비로 진공 증착하여 300 Å의 두께로 전자 주입 및 수송층을 형성했다. 상기 전자 주입 및 수송층 위에 순차적으로 12 Å 두께로 리튬플로라이드(LiF)와 1000 Å 두께로 알루미늄을 증착하여 음극을 형성했다. The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5% by weight. The following compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed by vacuum depositing the following compound EB-1 to a film thickness of 150 Å on the hole transport layer. Subsequently, on the EB-1 deposited film, Compound 1-1 and Compound 2-1 as hosts and Compound Dp-7 as a dopant were vacuum co-evaporated at a weight ratio of 49:49:2 to form a red light emitting layer having a thickness of 400 Å. . A hole blocking layer was formed on the light emitting layer by vacuum depositing the following compound HB-1 to a film thickness of 30 Å. Subsequently, the following compound ET-1 and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.
상기의 과정에서 유기물의 증착속도는 0.4 ~ 0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2ⅹ10-7 ~ 5ⅹ10-6 torr를 유지하여, 유기 발광 소자를 제작했다.In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å / sec, and the deposition rate of aluminum was 2 Å / sec, and the vacuum degree during deposition was 2 × 10 -7 While maintaining ~ 5ⅹ10 -6 torr, an organic light emitting device was fabricated.
실시예 2 내지 실시예 220Examples 2 to 220
실시예 1의 유기 발광 소자에서 화합물 1-1 및 화합물 2-1 대신 표 1 내지 표 5에 기재된 제1 호스트로 및 제2호스트를 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다. Except for using the first host and the second host described in Tables 1 to 5 instead of Compound 1-1 and Compound 2-1 in the organic light emitting device of Example 1, the organic light emitting device was prepared in the same manner as in Example 1. A light emitting device was manufactured.
비교예 1 내지 비교예 23Comparative Examples 1 to 23
실시예 1의 유기 발광 소자에서 화합물 1-1 및 화합물 2-1 대신 하기 표 6에 기재된 화합물만을 호스트로 사용하고 상기 호스트와 화합물 Dp-7을 98:2의 중량비로 진공 증착하여 발광층을 형성 하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다.In the organic light emitting device of Example 1, only the compounds listed in Table 6 were used instead of Compound 1-1 and Compound 2-1 as a host, and the host and Compound Dp-7 were vacuum deposited at a weight ratio of 98: 2 to form a light emitting layer. Except for the above, an organic light emitting device was manufactured in the same manner as in Example 1.
비교예 24 내지 비교예 51Comparative Examples 24 to 51
실시예 1의 유기 발광 소자에서 화합물 1-1 및 화합물 2-1 대신 하기 표 7에 기재된 화합물만을 호스트로 사용하고 상기 호스트와 화합물 Dp-7을 98:2의 중량비로 진공 증착하여 발광층을 형성 하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다.In the organic light emitting device of Example 1, only the compounds listed in Table 7 were used instead of Compound 1-1 and Compound 2-1 as a host, and the host and Compound Dp-7 were vacuum deposited at a weight ratio of 98: 2 to form a light emitting layer. Except for the above, an organic light emitting device was manufactured in the same manner as in Example 1.
실험예Experimental example
상기 실시예 1 내지 실시예 220 및 비교예 1 내지 비교예 51에서 제조한 유기 발광 소자에 전류를 인가하였을 때, 전압, 효율을 측정(15mA/cm2 기준)하고 그 결과를 하기 표1 내지 표4에 나타냈다. 수명 T95는 휘도가 초기 휘도(6,000 nit)에서 95%로 감소되는데 소요되는 시간을 의미한다.When current was applied to the organic light emitting devices prepared in Examples 1 to 220 and Comparative Examples 1 to 51, voltage and efficiency were measured (based on 15 mA/cm 2 ) and the results are shown in Tables 1 to 51 below. shown in 4. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nit) to 95%.
[표 1][Table 1]
[표 2][Table 2]
[표 3][Table 3]
[표 4][Table 4]
[표 5][Table 5]
[표 6][Table 6]
[표 7][Table 7]
실시예 1 내지 220 및 비교예 1 내지 51에 의해 제작된 유기 발광 소자에 전류를 인가하였을 때, 상기 표 1 내지 표 7의 결과를 얻었다. 상기 비교예 1의 적색 유기 발광 소자는 종래 널리 사용되고 있는 물질을 사용하였으며, 전자 차단층으로 화합물 EB-1, 적색 발광층 도펀트로 화합물 Dp-7을 사용하였다. 표 6에서와 같이 비교예 화합물로 본 발명의 화학식 2로 표시되는 화합물만을 발광층의 호스트로 사용했을 때 본 발명의 조합보다 대체적으로 구동전압은 상승하고 효율과 수명이 떨어지는 결과를 보였다. 표 7에서는 비교예 화합물로 본 발명의 화학식 1로 표시되는 화합물만을 발광층의 호스트로 사용했는데 화학식 2를 호스트로 사용했을 때보다는 구동전압, 효율, 수명이 개선되나 본 발명의 조합보다 동전압은 상승하고 효율과 수명이 떨어지는 결과를 보였다.When current was applied to the organic light emitting devices manufactured in Examples 1 to 220 and Comparative Examples 1 to 51, the results of Tables 1 to 7 were obtained. The red organic light emitting device of Comparative Example 1 used materials widely used in the prior art, and used compound EB-1 as an electron blocking layer and compound Dp-7 as a dopant for the red light emitting layer. As shown in Table 6, when only the compound represented by
이러한 결과들로부터 본 발명의 제1 호스트인 화학식 1로 표시되는 화합물과 제2 호스트인 화학식 2로 표시되는 화합물의 조합을 유기 발광 소자에 사용하는 경우 적색 발광층 내의 적색 도판트로의 에너지 전달이 잘 이루어져 구동 전압이 개선되고 효율 및 수명이 상승하는 것을 확인할 수 있었다. 이것은 결국 비교예 화합물과 같이 호스트로 단일 호스트로 사용한 것 보다 본 발명의 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물의 조합이 발광층 내에서 더 안정적인 균형을 통해 전자와 정공이 결합하여 엑시톤을 형성하여 효율과 수명이 상승하기 때문으로 파악된다. 결론적으로 본 발명의 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물을 조합하고 공증착하여 적색 발광층의 호스트로 사용하였을 때 유기 발광 소자의 구동전압, 발광 효율 및 수명 특성을 개선할 수 있다는 것을 확인할 수 있다. From these results, when the combination of the compound represented by
1: 기판
2: 양극
3: 발광층
4: 음극
5: 정공주입층
6: 정공수송층
7: 전자차단층
8: 정공저지층
9: 전자 주입 및 수송층1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: electron injection and transport layer
Claims (11)
음극; 및
상기 양극과 음극 사이의 발광층을 포함하고,
상기 발광층은 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물을 포함하는,
유기 발광 소자:
[화학식 1]
상기 화학식 1에서,
X1 내지 X7은 각각 독립적으로, CR1 또는 N이되, X1 내지 X7 중 적어도 하나는 N이고,
상기 R1은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,
L1 내지 L3는 각각 독립적으로, 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴렌이고,
Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,
[화학식 2]
상기 화학식 2에서,
Y1이 N이고, Y2가 O이거나; Y1이 O이고, Y2가 N이고,
R' 및 R'1 내지 R'6 중 어느 하나는 하기 화학식 2A로 표시되는 치환기이고, 나머지는 수소; 중수소; 또는 치환 또는 비치환된 C6-60 아릴이고,
[화학식 2A]
상기 화학식 2A에서,
L'1 내지 L'3은 각각 독립적으로, 단일결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,
Ar'1 및 Ar'2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이다.
anode;
cathode; and
Including a light emitting layer between the anode and the cathode,
The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.
Organic Light-Emitting Elements:
[Formula 1]
In Formula 1,
X 1 to X 7 are each independently CR 1 or N, but at least one of X 1 to X 7 is N;
The R 1 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
L 1 to L 3 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
[Formula 2]
In Formula 2,
Y 1 is N and Y 2 is O; Y 1 is O, Y 2 is N,
Any one of R' and R' 1 to R' 6 is a substituent represented by Formula 2A below, and the others are hydrogen; heavy hydrogen; or a substituted or unsubstituted C 6-60 aryl;
[Formula 2A]
In Formula 2A,
L' 1 to L' 3 are each independently a single bond; or a substituted or unsubstituted C 6-60 arylene;
Ar' 1 and Ar' 2 are each independently a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.
X1 내지 X7 중 어느 하나는 N이고, 나머지는 CR1인,
유기 발광 소자.
According to claim 1,
Any one of X 1 to X 7 is N and the others are CR 1 ,
organic light emitting device.
R1은 수소, 중수소, 페닐, 비페닐릴, 나프틸, 카바졸릴, 플루오란테닐, 페난트레닐, 트리페닐레닐, 벤조[a]카바졸릴, 벤조[b]카바졸릴, 벤조[c]카바졸릴, 디벤조퓨라닐, 벤조[d]나프토[1,2-b]퓨라닐, 벤조[d]나프토[2,3-b]퓨라닐, 벤조[d]나프토[2,1-b]퓨라닐, 벤조[d]나프토[1,2-b]티오페닐, 벤조[d]나프토[2,3-b]티오페닐, 벤조[d]나프토[2,1-b]티오페닐, 벤조[c]페난트레닐, 크라이세닐, 페닐 나프틸, 또는 나프틸 페닐이고,
상기 R1이 수소 또는 중수소가 아닌 경우 R1은 비치환되거나 1개 이상의 중수소로 치환되는,
유기 발광 소자.
According to claim 1,
R 1 is hydrogen, deuterium, phenyl, biphenylyl, naphthyl, carbazolyl, fluoranthenyl, phenanthrenyl, triphenylenyl, benzo[a]carbazolyl, benzo[b]carbazolyl, benzo[c]carba Zolyl, dibenzofuranil, benzo[d]naphtho[1,2-b]furanil, benzo[d]naphtho[2,3-b]furanil, benzo[d]naphtho[2,1- b] furanil, benzo[d]naphtho[1,2-b]thiophenyl, benzo[d]naphtho[2,3-b]thiophenyl, benzo[d]naphtho[2,1-b] thiophenyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, or naphthyl phenyl;
Where R 1 is not hydrogen or deuterium, R 1 is unsubstituted or substituted with one or more deuterium,
organic light emitting device.
L1 내지 L3는 각각 독립적으로, 단일결합, 페닐렌, 나프탈렌디일, , , 또는 이고,
상기 L1 내지 L3가 단일결합이 아닌 경우 L1 내지 L3는 비치환되거나 1개 이상의 중수소로 치환되는,
유기 발광 소자.
According to claim 1,
L 1 to L 3 are each independently a single bond, phenylene, naphthalenediyl, , , or ego,
Where L 1 to L 3 are not a single bond, L 1 to L 3 are unsubstituted or substituted with one or more deuterium atoms;
organic light emitting device.
Ar1 및 Ar2는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 플루오란테닐, 페난트레닐, 디벤조퓨라닐, 디벤조티오페닐, 크라이세닐, 또는 벤조[c]페난트레닐이고,
상기 Ar1 및 Ar2는 비치환되거나 1개 이상의 중수소로 치환되는,
유기 발광 소자.
According to claim 1,
Ar 1 and Ar 2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, fluoranthenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, chrysenyl, or benzo[c]phenane Trenyl,
Wherein Ar 1 and Ar 2 are unsubstituted or substituted with one or more deuterium,
organic light emitting device.
상기 화학식 1로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,
유기 발광 소자:
.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:
.
R' 및 R'1 내지 R'6 중 어느 하나는 하기 화학식 2A로 표시되는 치환기이고, 나머지는 수소; 중수소; 비치환되거나 1개 내지 5개의 중수소로 치환되는 페닐; 또는 비치환되거나 1개 내지 7개의 중수소로 치환되는 나프틸인,
유기 발광 소자.
According to claim 1,
Any one of R' and R' 1 to R' 6 is a substituent represented by Formula 2A below, and the others are hydrogen; heavy hydrogen; phenyl unsubstituted or substituted with 1 to 5 deuterium; or naphthyl, which is unsubstituted or substituted with 1 to 7 deuterium atoms;
organic light emitting device.
화학식 2는 하기 화학식 2-1 또는 화학식 2-2 중 어느 하나로 표시되는,
유기 발광 소자:
[화학식 2-1]
[화학식 2-2]
상기 화학식 2-1 및 화학식 2-2에서,
상기 Y1, Y2, R', L'1 내지 L'3, Ar'1 및 Ar'2는 제1항에서 정의한 바와 같다.
According to claim 1,
Formula 2 is represented by any one of Formula 2-1 or Formula 2-2,
Organic Light-Emitting Elements:
[Formula 2-1]
[Formula 2-2]
In Formula 2-1 and Formula 2-2,
The Y 1 , Y 2 , R', L' 1 to L' 3 , Ar' 1 and Ar' 2 are as defined in claim 1.
L'1 내지 L'3은 각각 독립적으로, 단일결합, 페닐렌, 비페닐디일, 터페닐디일, 나프탈렌디일, , , 또는 이고,
상기 L'1 내지 L'3이 단일결합이 아닌 경우, L'1 내지 L'3은 비치환되거나1개 이상의 중수소로 치환되는,
유기 발광 소자.
According to claim 1,
L' 1 to L' 3 are each independently a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthalenediyl, , , or ego,
When L' 1 to L' 3 are not a single bond, L' 1 to L' 3 are unsubstituted or substituted with one or more deuterium atoms,
organic light emitting device.
Ar'1 및 Ar'2는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난트레닐, 디벤조퓨라닐, 디벤조티오페닐, 디메틸플루오레닐, 카바졸릴, 또는 페닐 카바졸릴이고,
상기 Ar'1 및 Ar'2는 비치환되거나 1개 이상의 중수소로 치환되는,
유기 발광 소자.
According to claim 1,
Ar' 1 and Ar' 2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, carbazolyl, or phenyl carba sleepy,
Wherein Ar' 1 and Ar' 2 are unsubstituted or substituted with one or more deuterium,
organic light emitting device.
상기 화학식 2로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,
유기 발광 소자:
.According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:
.
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