TW202342695A - Boron-containing cyclic emissive compounds and color conversion film containing the same - Google Patents

Boron-containing cyclic emissive compounds and color conversion film containing the same Download PDF

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TW202342695A
TW202342695A TW112105757A TW112105757A TW202342695A TW 202342695 A TW202342695 A TW 202342695A TW 112105757 A TW112105757 A TW 112105757A TW 112105757 A TW112105757 A TW 112105757A TW 202342695 A TW202342695 A TW 202342695A
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郑世俊
傑弗瑞 漢默克
蔡潔
丁新亮
協 劉
王鵬
𦭑莎 姚
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日商日東電工股份有限公司
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Abstract

The present disclosure relates to novel photoluminescent complex comprising a BODIPY moiety covalently bonded to a blue light absorbing xanthenoisoquinoline derivative, a color conversion film comprising the photoluminescent complex, and a backlight unit using the same.

Description

含硼環狀發光化合物和含有該含硼環狀發光化合物的色轉換膜Boron-containing cyclic luminescent compound and color conversion film containing the boron-containing cyclic luminescent compound

本發明係關於用於色轉換膜之化合物,以及包括該色轉換膜之背光單元及顯示設備。The present invention relates to compounds used in color conversion films, as well as backlight units and display devices including the color conversion films.

除非本發明中另外指示,否則本發明中所描述之材料並非本申請案中之申請專利範圍的先前技術,且不因包括在此部分中而承認其為先前技術。Unless otherwise indicated herein, the material described in this disclosure is not prior art to the patentable scope of this application and is not admitted to be prior art by inclusion in this section.

在色彩再現中,色域(gamut/color gamut)為在諸如電視或監視器之裝置上可供使用的色彩之某一完整子集。舉例而言,已開發出Adobe TMRed Green Blue (RGB),一種藉由使用純光譜原色實現之寬色域色彩空間,以提供較廣色域且提供經由顯示器觀看之可見色彩的更真實呈現。咸信,可提供較寬色域之裝置可使得顯示器能夠描繪更鮮明的色彩。 In color reproduction, a color gamut is a complete subset of the colors available on a device such as a television or monitor. For example, Adobe Red Green Blue (RGB), a wide gamut color space implemented by using pure spectral primary colors, has been developed to provide a wider color gamut and a more realistic representation of visible colors viewed through a monitor. It is believed that devices that offer a wider color gamut will allow displays to depict more vivid colors.

隨著高清晰度大螢幕顯示器變得愈加普遍,人們對更高效能、更輕薄及高功能性的顯示器的需求增加。當前的發光二極體(LED)係藉由激發綠色磷光體、紅色磷光體或黃色磷光體以獲得白光光源之藍光光源獲得。然而,當前綠色及紅色磷光體之發射峰之全寬半高值(FWHM)相當大,通常大於40 nm,使得綠色及紅色光譜重疊且呈現出彼此無法完全區分的色彩。此重疊導致色彩再現不佳以及色域之劣化。As high-definition large-screen displays become more common, demand for more efficient, thinner and more functional displays increases. Current light-emitting diodes (LEDs) are obtained by using a blue light source that excites a green phosphor, a red phosphor, or a yellow phosphor to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is quite large, usually greater than 40 nm, causing the green and red spectra to overlap and present colors that are not completely distinguishable from each other. This overlap results in poor color reproduction and degradation of the color gamut.

為了校正色域之劣化,已開發出使用含有量子點與LED之組合的膜的方法。然而,量子點具有多種缺點,包括毒性、效率低、封裝製程昂貴及尺寸均勻性。In order to correct the degradation of the color gamut, methods have been developed using films containing a combination of quantum dots and LEDs. However, quantum dots suffer from various disadvantages, including toxicity, low efficiency, expensive packaging process, and size uniformity.

因此,需要改良色轉換膜、背光單元及顯示裝置之效能。Therefore, there is a need to improve the performance of color conversion films, backlight units and display devices.

本文所描述之光致發光複合物可用於改良電視、電腦監視器、智慧型裝置及利用彩色顯示器之任何其他裝置中之可區分色彩之間的對比度。本發明之光致發光複合物提供具有良好藍光吸收率及窄發射頻寬的新的色轉換染料,其中發射頻帶之全寬半高值[FWHM]小於40 nm。在一些實施例中,光致發光複合物吸收第一波長之光且發射高於第一波長之第二波長的光。本文所揭示之光致發光複合物可與用於發光設備之色轉換膜一起使用。本發明之色轉換膜藉由減少色彩光譜內之重疊而減少色彩劣化,從而產生高品質色彩再現。The photoluminescent compounds described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other device utilizing color displays. The photoluminescent composite of the present invention provides a new color conversion dye with good blue light absorption and a narrow emission bandwidth, in which the full width at half maximum [FWHM] of the emission band is less than 40 nm. In some embodiments, the photoluminescent composite absorbs light at a first wavelength and emits light at a second wavelength higher than the first wavelength. The photoluminescent composites disclosed herein can be used with color conversion films for light emitting devices. The color conversion film of the present invention reduces color degradation by reducing overlap within the color spectrum, thereby producing high quality color reproduction.

一些實施例包括一種光致發光複合物,其包含:吸收藍光之呫噸并異喹啉衍生物;連接子複合物,其包含未經取代之酯或經取代之酯;及硼-二吡咯亞甲基(BODIPY)部分。在一些實施例中,連接子複合物可共價連接呫噸并異喹啉衍生物與BODIPY部分。在一些實施例中,呫噸并異喹啉衍生物吸收第一激發波長之光能且將能量傳遞至BODIPY部分。在一些實施例中,BODIPY部分吸收來自呫噸并異喹啉衍生物之能量且發射第二較高波長之光能。在一些實施例中,光致發光複合物具有大於80%之發射量子產率。Some embodiments include a photoluminescent complex comprising: a blue light-absorbing xanthenoisoquinoline derivative; a linker complex comprising an unsubstituted ester or a substituted ester; and boron-dipyrrolidine. Methyl (BODIPY) moiety. In some embodiments, the linker complex can covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy at the first excitation wavelength and transfers the energy to the BODIPY moiety. In some embodiments, BODIPY partially absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second higher wavelength. In some embodiments, the photoluminescent composite has an emission quantum yield greater than 80%.

在一些實施例中,光致發光複合物可具有全寬半高值[FWHM]至多40 nm之發射頻帶。In some embodiments, the photoluminescent composite can have an emission band with a full width at half maximum [FWHM] of up to 40 nm.

在一些實施例中,光致發光複合物可具有等於或大於45 nm之斯托克位移(stoke shift),亦即藍光吸收部分之激發峰與BODIPY部分之發射峰之間的差值。In some embodiments, the photoluminescent composite may have a stoke shift equal to or greater than 45 nm, ie, the difference between the excitation peak of the blue light absorbing portion and the emission peak of the BODIPY portion.

在一些實施例中,光致發光複合物可具有下式: In some embodiments, the photoluminescent composite can have the following formula:

在一些實施例中,呫噸并異喹啉衍生物可具有以下通式: ,其中R 9為H、C 1-C 4烷基或視情況經取代之芳基,其中經取代之官能基可為視情況經取代之C 1-C 3甲基,例如三氟甲基(-CF 3)。 In some embodiments, the xanthenoisoquinoline derivative can have the following general formula: , wherein R 9 is H, C 1 -C 4 alkyl or optionally substituted aryl, wherein the substituted functional group can be optionally substituted C 1 -C 3 methyl, such as trifluoromethyl ( -CF 3 ).

一些實施例包括一種色轉換膜,其包含:透明基板層;色轉換層;及至少一種光致發光複合物。在一些實施例中,色轉換層可包含樹脂基質。在一些實施例中,至少一種光致發光複合物分散於樹脂基質內。在一些實施例中,樹脂基質可包含聚(丙烯酸丁酯)。在一些實施例中,色轉換膜可包含10 µm至約200 µm之厚度。在一些實施例中,本發明之色轉換膜可吸收400 nm至約480 nm範圍內之藍光且發射510 nm至約560 nm波長範圍內之光。另一實施例包括一種可吸收400 nm至約480 nm範圍內之藍光且發射575 nm至約645 nm波長範圍內之光的色轉換膜。在一些實施例中,色轉換膜可進一步包含透明基板層。在一些實施例中,透明基板層包含兩個相對表面,其中色轉換層安置於相對表面中之一者上。Some embodiments include a color conversion film comprising: a transparent substrate layer; a color conversion layer; and at least one photoluminescent composite. In some embodiments, the color conversion layer may include a resin matrix. In some embodiments, at least one photoluminescent composite is dispersed within a resin matrix. In some embodiments, the resin matrix may include poly(butyl acrylate). In some embodiments, the color conversion film may include a thickness of 10 µm to about 200 µm. In some embodiments, the color conversion film of the present invention can absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 510 nm to about 560 nm. Another embodiment includes a color conversion film that absorbs blue light in the range of 400 nm to about 480 nm and emits light in the wavelength range of 575 nm to about 645 nm. In some embodiments, the color conversion film may further include a transparent substrate layer. In some embodiments, the transparent substrate layer includes two opposing surfaces, with the color conversion layer disposed on one of the opposing surfaces.

一些實施例包括一種用於製備色轉換膜之方法,該方法包含:將光致發光複合物及黏合劑樹脂溶解於溶劑內;及將混合物塗覆於透明基板相對表面中之一者上。Some embodiments include a method for preparing a color conversion film, the method comprising: dissolving a photoluminescent composite and a binder resin in a solvent; and coating the mixture on one of opposing surfaces of a transparent substrate.

一些實施例包括一種背光單元,其包含本文所描述之色轉換膜。Some embodiments include a backlight unit including a color conversion film described herein.

一些實施例包括一種顯示裝置,其包含本文所描述之背光單元。Some embodiments include a display device including a backlight unit described herein.

本申請案提供一種具有極佳色域及發光特性之光致發光複合物、一種製造包含該等光致發光複合物之色轉換膜的方法以及一種包含該色轉換膜之背光單元。下文更詳細地描述此等及其他實施例。The present application provides a photoluminescent composite with excellent color gamut and luminescence characteristics, a method of manufacturing a color conversion film including the photoluminescent composite, and a backlight unit including the color conversion film. These and other embodiments are described in greater detail below.

本發明係關於光致發光含硼環狀發光複合物以及其在色轉換膜、背光單元及顯示裝置中之用途。此等複合物通常更簡單地稱為光致發光複合物。光致發光複合物可用於改良及增強一或多個所需發射頻寬在色轉換膜內之透射。在一些實施例中,光致發光複合物可既增強所需第一發射頻寬之透射且亦減少第二發射頻寬之透射。舉例而言,色轉換膜可增強兩種或更多種色彩之間的對比度或強度,從而增加彼此之區別。本發明亦包括用於製備本文所描述之色轉換膜的方法。The present invention relates to photoluminescent boron-containing cyclic luminescent composites and their use in color conversion films, backlight units and display devices. Such complexes are often more simply referred to as photoluminescent complexes. Photoluminescent compounds can be used to modify and enhance the transmission of one or more desired emission bandwidths within the color conversion film. In some embodiments, the photoluminescent composite can both enhance transmission in a desired first emission bandwidth and reduce transmission in a second emission bandwidth. For example, color conversion films can enhance the contrast or intensity between two or more colors, thereby increasing their distinction from each other. The present invention also includes methods for preparing the color conversion films described herein.

如本文所使用,當化合物或化學結構被稱為「經取代」或「視情況經取代」時,其可包括一或多個取代基。經取代之基團衍生自未經取代之母結構,其中母結構上之一或多個氫原子已獨立地經一或多個取代基置換。在一或多種形式中,取代基可獨立地選自視情況經取代之烷基、烯基或C 3-C 7雜烷基。 As used herein, when a compound or chemical structure is referred to as "substituted" or "optionally substituted," it may include one or more substituents. Substituted groups are derived from an unsubstituted parent structure in which one or more hydrogen atoms on the parent structure have been independently replaced with one or more substituents. In one or more forms, substituents may be independently selected from optionally substituted alkyl, alkenyl, or C 3 -C 7 heteroalkyl.

如本文所使用之術語「烷基」係指脂族烴基。烷基可為「飽和烷基」,此意謂其並不含有任何烯烴或炔烴部分。烷基部分亦可為「不飽和烷基」部分,此意謂其含有至少一個烯烴或炔烴部分。「烯烴」部分係指具有至少一個碳-碳雙鍵(-C=C-)之基團,且「炔烴」部分係指具有至少一個碳-碳參鍵(-C≡C-)之基團。不論飽和或不飽和,烷基部分可為分支鏈、直鏈或環狀的。The term "alkyl" as used herein refers to an aliphatic hydrocarbon group. An alkyl group can be a "saturated alkyl group," meaning that it does not contain any alkene or alkyne moiety. The alkyl moiety may also be an "unsaturated alkyl" moiety, meaning that it contains at least one alkene or alkyne moiety. The "alkene" moiety refers to a group having at least one carbon-carbon double bond (-C=C-), and the "alkyne" moiety refers to a group having at least one carbon-carbon double bond (-C≡C-) group. Whether saturated or unsaturated, the alkyl moiety can be branched, straight chain or cyclic.

烷基部分可具有1至6個碳原子(無論其是否在本文中出現,諸如「1至6」之數值範圍係指給定範圍中之各整數:例如「1至6個碳原子」意謂烷基可具有1個碳原子、2個碳原子、3個碳原子等,至多(且包括) 6個碳原子,但本發明定義亦包括未指定數值範圍之術語「烷基」的存在)。本文中指定之化合物之烷基可指定為「C 1-C 6烷基」或類似名稱。僅藉助於實例,「C 1-C 6烷基」指示烷基鏈中存在一至六個碳原子,亦即烷基鏈為甲基、乙基、丙基、異丙基、正丁基、異丁基、二級丁基或三級丁基。因此,C 1-C 6烷基包括C 1-C 2烷基、C 1-C 3烷基、C 1-C 4烷基、C 1-C 5烷基。烷基可經取代或未經取代。典型的烷基包括(但不限於)甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、己基、乙烯基、丙烯基、丁烯基、環丙基、環丁基、環戊基、環己基及其類似基團。 The alkyl moiety may have from 1 to 6 carbon atoms (whether or not it appears herein, numerical ranges such as "1 to 6" refer to each integer within the given range: for example, "1 to 6 carbon atoms" means Alkyl groups may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, but the present definition also includes the presence of the term "alkyl" without specifying a numerical range). Alkyl groups of compounds designated herein may be designated "C 1 -C 6 alkyl" or similar designations. By way of example only, "C 1 -C 6 alkyl" indicates the presence of one to six carbon atoms in the alkyl chain, i.e. the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, iso Butyl, secondary butyl or tertiary butyl. Thus, C 1 -C 6 alkyl includes C 1 -C 2 alkyl, C 1 -C 3 alkyl, C 1 -C 4 alkyl, C 1 -C 5 alkyl. Alkyl groups may be substituted or unsubstituted. Typical alkyl groups include (but are not limited to) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, vinyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and similar groups.

如本文所使用,術語「雜烷基」係指其中組分碳原子中之一或多者已經氮、氧或硫置換的如本文所定義之烷基。實例包括(但不限於) -CH 2-O-CH 3、-CH 2-CH 2-O-CH 3、-CH 2-NH-CH 3、-CH 2-N(CH 3)-CH 3、-CH 2-CH 2-NH-CH 3、-CH 2-CH 2-N(CH 3)-CH 3、-CH 2-S-CH 2-CH 3、-CH 2-CH 2-S(O)-CH 3。另外,至多兩個雜原子可鄰接,諸如(藉助於實例) -CH 2-NH-O-CH 3等。 As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more of the component carbon atoms have been replaced with nitrogen, oxygen, or sulfur. Examples include (but are not limited to) -CH 2 -O-CH 3 , -CH 2 -CH 2 -O-CH 3 , -CH 2 -NH-CH 3 , -CH 2 -N(CH 3 )-CH 3 , -CH 2 -CH 2 -NH-CH 3 , -CH 2 -CH 2 -N(CH 3 )-CH 3 , -CH 2 -S-CH 2 -CH 3 , -CH 2 -CH 2 -S(O )-CH 3 . Additionally, up to two heteroatoms may be adjacent, such as (by way of example) -CH2 -NH-O- CH3 , etc.

術語「芳族」係指具有非定域π電子系統之平面環,該系統含有4n+2個π電子,其中n為整數。芳族環可由五個、六個、七個、八個、九個或多於九個原子形成。芳族物可視情況經取代。術語「芳族」包括碳環芳基(例如苯基)及雜環芳基(或「雜芳基」或「雜芳族基」) (例如吡啶)兩者。該術語包括單環或稠合環多環(亦即,共用相鄰碳原子對之環)基團。The term "aromatic" refers to a planar ring having a delocalized pi electron system containing 4n+2 pi electrons, where n is an integer. Aromatic rings may be formed from five, six, seven, eight, nine or more than nine atoms. Aromatics may be optionally substituted. The term "aromatic" includes both carbocyclic aryl groups (eg, phenyl) and heterocyclic aryl groups (or "heteroaryl" or "heteroaryl") (eg, pyridine). The term includes monocyclic or fused cyclic polycyclic (ie, rings that share pairs of adjacent carbon atoms) groups.

如本文所使用之術語「芳基」意謂其中形成環之原子中之各者均為碳原子的芳族環。芳基環可由五個、六個、七個、八個或多於八個碳原子形成。芳基可經取代或未經取代。芳基之實例包括(但不限於)苯基、萘基、菲基等。The term "aryl" as used herein means an aromatic ring in which each of the atoms forming the ring is a carbon atom. Aryl rings can be formed from five, six, seven, eight, or more than eight carbon atoms. Aryl groups may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, and the like.

術語「芳烷基」係指經如本文所定義之芳基取代的如本文所定義之烷基。非限制性芳烷基包括苯甲基、苯乙基及其類似基團。The term "aralkyl" refers to an alkyl group as defined herein substituted with an aryl group as defined herein. Non-limiting aralkyl groups include benzyl, phenethyl and the like.

如本文所使用之術語「鹵素」意謂氟、氯、溴及碘。The term "halogen" as used herein means fluorine, chlorine, bromine and iodine.

如本文所使用之術語「鍵」、「鍵結」、「直接鍵」或「單鍵」意謂兩個原子之間的化學鍵,或當藉由鍵接合之原子被視為較大結構之一部分時與兩個部分之化學鍵。As used herein, the terms "bond", "bond", "direct bond" or "single bond" mean a chemical bond between two atoms, or when the atoms joined by a bond are considered to be part of a larger structure time and the chemical bond between the two parts.

如本文所使用之術語「部分」係指分子之特定區段或官能基。化學部分為嵌入分子中或附接至分子之通常公認之化學實體。The term "portion" as used herein refers to a specific segment or functional group of a molecule. A chemical moiety is a generally recognized chemical entity embedded in or attached to a molecule.

術語「酯」係指具有式-COOR之化學部分,其中R為烷基、環烷基、芳基、雜芳基(經由環碳鍵結)或雜環(經由環碳鍵結)。本文所描述之化合物上之任何羥基或羧基側鏈可經酯化。可使用任何適合之方法來製備本發明之酯。The term "ester" refers to a chemical moiety of the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded via a ring carbon) or heterocycle (bonded via a ring carbon). Any hydroxyl or carboxyl side chain on the compounds described herein can be esterified. Any suitable method may be used to prepare the esters of the present invention.

術語「可(may)」或「可(may be)」應被視作「為(is)」或「不為(is not)」或者「進行(does)」或「不進行(does not)」或「會(will)」或「不會(will not)」等之簡寫形式。舉例而言,陳述「色轉換膜可包含透明基板層」應解釋為例如「在一些實施例中,色轉換膜包含透明基板層」或「在一些實施例中,色轉換膜不包含透明基板層」。The terms "may" or "may be" shall be read as "is" or "is not" or "does" or "does not" Or the abbreviation of "will" or "will not". For example, the statement "the color conversion film may include a transparent substrate layer" should be interpreted to mean, for example, "In some embodiments, the color conversion film includes a transparent substrate layer" or "In some embodiments, the color conversion film does not include a transparent substrate layer" ”.

如本文所使用之術語「BODIPY」係指具有下式之化學部分: , 其包含與經二取代之硼原子(通常為BF 2單元)複合的二吡咯亞甲基。BODIPY核心之IUPAC名稱為4,4-二氟-4-硼雜-3a,4a-二氮雜-s-茚烯。在一些實施例中,L為連接子複合物。 The term "BODIPY" as used herein refers to a chemical moiety having the formula: , which contains a dipyrromethene group complexed with a disubstituted boron atom (usually a BF 2 unit). The IUPAC name of the core of BODIPY is 4,4-difluoro-4-bora-3a,4a-diaza-s-indenene. In some embodiments, L is a linker complex.

如本文所使用之術語「呫噸并異喹啉」或「呫噸并異喹啉衍生物」或「XI」係指具有下式之化學部分: 。 呫噸并異喹啉核心之IUPAC名稱為1H-呫噸并[2,1,9-def]異喹啉-1,3(2H)-二酮。 The term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" or "XI" as used herein refers to a chemical moiety having the formula: . The IUPAC name of the xanthenoisoquinoline core is 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

本發明係關於光致發光複合物,其吸收第一波長之光能且發射第二較高波長之光能。本發明之光致發光複合物包含吸收發光部分及發射發光部分,其經由連接子偶合,使得其距離針對吸收發光部分最佳化以將其能量傳遞至受體發光部分,其中受體發光部分隨後發射比所吸收之第一波長更大的第二波長之能量。The present invention relates to photoluminescent composites that absorb light energy at a first wavelength and emit light energy at a second, higher wavelength. The photoluminescent composites of the present invention comprise an absorbing luminescent moiety and an emitting luminescent moiety coupled via a linker such that their distance is optimized for the absorbing luminescent moiety to transfer its energy to an acceptor luminescent moiety, wherein the acceptor luminescent moiety then Emit a second wavelength of energy greater than the absorbed first wavelength.

一些實施例包括一種光致發光複合物。在一些實施例中,光致發光複合物包含:吸收藍光之呫噸并異喹啉衍生物;連接子複合物;及硼-二吡咯亞甲基(BODIPY)部分。在一些實施例中,連接子複合物可將呫噸并異喹啉衍生物共價連接至BODIPY部分。在一些實施例中,光致發光複合物可由式B-L-X表示,其中B為BODIPY部分,L為連接子複合物,且X為呫噸并異喹啉衍生物。在一些實施例中,光致發光複合物可由以下化學式表示: Some embodiments include a photoluminescent composite. In some embodiments, the photoluminescent complex includes: a blue light-absorbing xanthenoisoquinoline derivative; a linker complex; and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker complex can covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the photoluminescent complex can be represented by the formula BLX, where B is a BODIPY moiety, L is a linker complex, and X is a xanthenoisoquinoline derivative. In some embodiments, the photoluminescent composite can be represented by the following chemical formula:

在一些實施例中,呫噸并異喹啉衍生物吸收第一激發波長之光且將能量傳遞至BODIPY部分,其中BODIPY部分隨後發射高於第一波長之第二波長的光能。咸信,自經激發之呫噸并異喹啉衍生物至BODIPY部分之能量傳遞係經由Förster共振能量傳遞(FRET)發生。此認為係歸因於光致發光複合物之吸收/發射光譜,其中存在兩個主要吸收頻帶,一個在藍光吸收頻帶處(呫噸并異喹啉衍生物)且一個在BODIPY吸收頻帶處,且僅存在一個發射頻帶,其位於BODIPY部分之發射波長處(參見 1 2)。 In some embodiments, the xanthenoisoquinoline derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, where the BODIPY moiety then emits light energy at a second wavelength greater than the first wavelength. It is believed that energy transfer from the excited xanthenoisoquinoline derivatives to the BODIPY moiety occurs via Förster resonance energy transfer (FRET). This is believed to be due to the absorption/emission spectrum of the photoluminescent composite, in which there are two main absorption bands, one at the blue light absorption band (xanthenoisoquinoline derivatives) and one at the BODIPY absorption band, and There is only one emission band, which is located at the emission wavelength of the BODIPY portion (see Figures 1 and 2 ).

在一實施例中,光致發光複合物可具有高發射量子產率。在一些實施例中,發射量子產率可大於約50%、約55%、約60%、約65%、或約70%、約75%、約80%、約85%、約90%、或約90%。發射量子產率可藉由用所吸收光子之數目除所發射光子之數目來量測,其等於發光部分之發射效率。在一些實施例中,吸收發光部分可具有大於80%之發射量子產率。在一些實施例中,量子產率可大於0.8 (80%)、0.81 (81%)、0.82 (82%)、0.83 (83%)、0.84 (84%)、0.85 (85%)、0.86 (86%)、0.87 (87%)、0.88 (88%)、0.89 (89%)、0.9 (90%)、0.91 (91%)、0.92 (92%)、0.93 (93%)、0.94 (94%)、0.95 (95%)或高達接近100%。膜中之量子產率量測可藉由分光光度計,例如Quantaurus-QY分光光度計(Hamamatsu, Inc., Campbell, CA, USA)進行。In one embodiment, the photoluminescent composite can have a high emission quantum yield. In some embodiments, the emission quantum yield can be greater than about 50%, about 55%, about 60%, about 65%, or about 70%, about 75%, about 80%, about 85%, about 90%, or About 90%. The emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equal to the emission efficiency of the luminescent part. In some embodiments, the absorbing luminescence moiety may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield can be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86 %), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%) , 0.95 (95%) or up to nearly 100%. Quantum yield measurements in films can be performed with a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

在一些實施例中,光致發光複合物具有發射頻帶,其中該發射頻帶可具有小於40 nm之全寬半高值(FWHM)。FWHM為在等於發射頻帶之最大發射強度之二分之一的發射強度下該頻帶之寬度,以奈米為單位。在一些實施例中,光致發光複合物具有小於或等於約35 nm、小於或等於約30 nm、小於或等於約25 nm、小於或等於約20 nm之發射頻帶FWHM值。在一些實施例中,FWHM為約20 nm至約25 nm、約25至30 nm、約30至35 nm、或約35至40 nm。In some embodiments, the photoluminescent composite has an emission band, wherein the emission band can have a full width at half maximum (FWHM) of less than 40 nm. FWHM is the width, in nanometers, of the emission band at an emission intensity equal to one-half the maximum emission intensity of the band. In some embodiments, the photoluminescent composite has an emission band FWHM value of less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, less than or equal to about 20 nm. In some embodiments, the FWHM is about 20 nm to about 25 nm, about 25 to 30 nm, about 30 to 35 nm, or about 35 to 40 nm.

在一些實施例中,光致發光複合物可具有等於或大於45 nm之斯托克位移。如本文所使用,術語「斯托克位移」意謂光致發光複合物(或其部分)之激發峰與光致發光複合物(或其部分)之發射峰之間的距離。在一些實施例中,光致發光複合物之斯托克位移可為約45至50 nm、約50至55 nm、約55至60 nm、約60至65 nm、約65至70 nm、約70至75 nm、約75至80 nm、約80至85 nm、約85至90 nm、約90至95 nm、約95至100 nm、或大於約100 nm,或在由此等值中之任一者限定之範圍內的任何數目。在一些實施例中,光致發光複合物之斯托克位移可大於100 nm、大於120 nm、大於130、大於140 nm、大於150 nm、或大於170 nm。舉例而言,藍光吸收部分與BODIPY部分之發射峰之間的斯托克位移可為本文所揭示之任何數目或範圍。In some embodiments, the photoluminescent composite can have a Stoke shift equal to or greater than 45 nm. As used herein, the term "Stokes shift" means the distance between the excitation peak of the photoluminescent complex (or a portion thereof) and the emission peak of the photoluminescent complex (or a portion thereof). In some embodiments, the Stoke shift of the photoluminescent composite can be about 45 to 50 nm, about 50 to 55 nm, about 55 to 60 nm, about 60 to 65 nm, about 65 to 70 nm, about 70 to 75 nm, about 75 to 80 nm, about 80 to 85 nm, about 85 to 90 nm, about 90 to 95 nm, about 95 to 100 nm, or greater than about 100 nm, or at any of these equivalent values any number within the limits of In some embodiments, the photoluminescent composite may have a Stoke shift greater than 100 nm, greater than 120 nm, greater than 130, greater than 140 nm, greater than 150 nm, or greater than 170 nm. For example, the Stoke shift between the blue light absorbing portion and the emission peak of the BODIPY portion can be any number or range disclosed herein.

在一些實施例中,本發明之光致發光複合物可具有可調諧(或可調節)的發射波長。在一些實施例中,在BODIPY部分上使用不同取代基可在約610 nm與約645 nm之間調節發射波長。在一些實例中,光致發光複合物之發射峰波長可在約610 nm至約645 nm、約610至615 nm、約615至620 nm、約620至625 nm、約625至630 nm、約630至635 nm、約635至640 nm、約640至645 nm之間,或為由此等值中之任一者限定之範圍內的任何波長。In some embodiments, the photoluminescent composites of the present invention may have tunable (or adjustable) emission wavelengths. In some embodiments, the use of different substituents on the BODIPY moiety can tune the emission wavelength between about 610 nm and about 645 nm. In some examples, the emission peak wavelength of the photoluminescent composite can be about 610 nm to about 645 nm, about 610 to 615 nm, about 615 to 620 nm, about 620 to 625 nm, about 625 to 630 nm, about 630 nm. to 635 nm, about 635 to 640 nm, about 640 to 645 nm, or any wavelength within the range defined by any of these equivalent values.

在一些實施例中,光致發光複合物可吸收一或多個波長下之光能。在一些實施例中,光致發光複合物之呫噸并異喹啉部分可吸收光。在一些實施例中,光致發光複合物之BODIPY部分可吸收光。在一些實施例中,光致發光複合物之BODIPY部分及光致發光複合物之呫噸并異喹啉部分均可吸收光。在一些實施例中,光致發光複合物之吸收藍光之呫噸并異喹啉部分可具有約400 nm至約470 nm之間的峰值吸收最大波長。在一些實施例中,峰值吸收可在約400 nm至約405 nm、約405至410 nm、約410至415 nm、約415至420 nm、約420至425 nm、約425至430 nm、約430至435 nm、約435至440 nm、約440至445 nm、約445至450 nm、約450至455 nm、約455至460 nm、約460至465 nm、約465至470 nm之間,或為由此等值中之任一者限定之範圍內的任何波長。在一些實施例中,光致發光複合物之BODIPY部分之峰值吸收最大波長可在約500 nm至約600 nm、約500至510 nm、約510至520 nm、約520至530 nm、約530至540 nm、約540至550 nm、約550至555 nm、約555至560 nm、約560至565 nm、約565至570 nm、約570至575 nm、約575至585 nm、約585至590 nm、約590至600 nm之間,或為由此等值中之任一者限定之範圍內的任何波長。在一些實施例中,光致發光複合物之吸收波長可在約400 nm至約405 nm、約405至410 nm、約410至415 nm、約415至420 nm、約420至425 nm、約425至430 nm、約430至435 nm、約435至440 nm、約440至445 nm、約445至450 nm、約450至455 nm、約455至460 nm、約460至465 nm、約465至470 nm、約500至600 nm、約500至510 nm、約510至520 nm、約520至530 nm、約530至540 nm、約540至550 nm、約550至555 nm、約555至560 nm、約560至565 nm、約565至570 nm、約570至575 nm、約575至585 nm、約585至590 nm、約590至600 nm之間,或為由此等值中之任一者限定之範圍內的任何波長。In some embodiments, the photoluminescent composite can absorb light energy at one or more wavelengths. In some embodiments, the xanthenoisoquinoline portion of the photoluminescent composite absorbs light. In some embodiments, the BODIPY portion of the photoluminescent composite can absorb light. In some embodiments, both the BODIPY portion of the photoluminescent composite and the xanthenoisoquinoline portion of the photoluminescent composite can absorb light. In some embodiments, the blue light-absorbing xanthenoisoquinoline portion of the photoluminescent composite may have a peak absorption maximum wavelength between about 400 nm and about 470 nm. In some embodiments, peak absorption can be at about 400 nm to about 405 nm, about 405 to 410 nm, about 410 to 415 nm, about 415 to 420 nm, about 420 to 425 nm, about 425 to 430 nm, about 430 nm. to 435 nm, about 435 to 440 nm, about 440 to 445 nm, about 445 to 450 nm, about 450 to 455 nm, about 455 to 460 nm, about 460 to 465 nm, about 465 to 470 nm, or between Any wavelength within the range defined by any of these equivalent values. In some embodiments, the peak absorption maximum wavelength of the BODIPY portion of the photoluminescent composite can be between about 500 nm to about 600 nm, about 500 to 510 nm, about 510 to 520 nm, about 520 to 530 nm, about 530 to 540 nm, about 540 to 550 nm, about 550 to 555 nm, about 555 to 560 nm, about 560 to 565 nm, about 565 to 570 nm, about 570 to 575 nm, about 575 to 585 nm, about 585 to 590 nm , between about 590 and 600 nm, or any wavelength within the range defined by any of these equivalent values. In some embodiments, the absorption wavelength of the photoluminescent composite can be about 400 nm to about 405 nm, about 405 to 410 nm, about 410 to 415 nm, about 415 to 420 nm, about 420 to 425 nm, about 425 nm. to 430 nm, about 430 to 435 nm, about 435 to 440 nm, about 440 to 445 nm, about 445 to 450 nm, about 450 to 455 nm, about 455 to 460 nm, about 460 to 465 nm, about 465 to 470 nm, about 500 to 600 nm, about 500 to 510 nm, about 510 to 520 nm, about 520 to 530 nm, about 530 to 540 nm, about 540 to 550 nm, about 550 to 555 nm, about 555 to 560 nm, Between about 560 to 565 nm, about 565 to 570 nm, about 570 to 575 nm, about 575 to 585 nm, about 585 to 590 nm, about 590 to 600 nm, or defined by any one of these equivalent values any wavelength within the range.

其他實施例包括光致發光複合物,其中吸收藍光之呫噸并異喹啉衍生物與BODIPY部分之空間距離經由連接子複合物調節,以改良吸收藍光之呫噸并異喹啉衍生物之能量至BODIPY部分的傳遞。在一些實施例中,連接子複合物共價連接吸收藍光之呫噸并異喹啉衍生物與BODIPY部分。在一些實施例中,呫噸并異喹啉衍生物吸收第一激發波長之光能且將能量傳遞至BODIPY部分,其中BODIPY部分吸收來自呫噸并異喹啉衍生物之能量且發射第二較高波長之光能。在一些實施例中,光致發光複合物具有大於80%之發射量子產率。Other embodiments include photoluminescent complexes in which the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety is adjusted via a linker complex to modify the energy of the blue light absorbing xanthenoisoquinoline derivative Pass to the BODIPY section. In some embodiments, the linker complex covalently links a blue light absorbing xanthenoisoquinoline derivative to a BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to a BODIPY moiety, wherein the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits a second excitation wavelength. High wavelength light energy. In some embodiments, the photoluminescent composite has an emission quantum yield greater than 80%.

一些實施例包括吸收藍光之呫噸并異喹啉衍生物(XI衍生物),其中吸收藍光之呫噸并異喹啉衍生物可具有以下通式: , 其中R 9可獨立地為H、甲基或視情況經取代之芳基,且R 10可獨立地為H、C 1-4烷基或視情況經取代之芳基。在一些實施例中,視情況經取代之芳基可為經取代之苯基或苯甲基。在一些實施例中,芳基可經三氟甲基部分取代。在一些實施例中,經取代之芳基可為 Some embodiments include blue light absorbing xanthenoisoquinoline derivatives (XI derivatives), wherein the blue light absorbing xanthenoisoquinoline derivative may have the following general formula: , wherein R 9 may be independently H, methyl or optionally substituted aryl, and R 10 may be independently H, C 1-4 alkyl or optionally substituted aryl. In some embodiments, the optionally substituted aryl group can be substituted phenyl or benzyl. In some embodiments, an aryl group can be substituted with a trifluoromethyl moiety. In some embodiments, the substituted aryl group can be , or .

連接子複合物L共價連接吸收藍色之呫噸并異喹啉衍生物與BODIPY部分。可調節連接子複合物以最佳化吸收藍光之呫噸并異喹啉衍生物與BODIPY部分之間的空間距離。藉由調節呫噸并異喹啉衍生物與BODIPY部分之間的空間距離,可改良量子產率。在一些實施例中,吸收藍光之呫噸并異喹啉衍生物與BODIPY部分之分隔距離可為約8 Å或更大。連接子複合物可維持吸收藍光之呫噸并異喹啉衍生物與BODIPY部分之間的距離。在其他實施例中,連接子複合物可包含呫噸并異喹啉衍生物與BODIPY部分之間的單鍵。The linker complex L covalently connects the blue-absorbing xanthenoisoquinoline derivative to the BODIPY moiety. The linker complex can be tuned to optimize the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. By adjusting the spatial distance between the xanthenoisoquinoline derivative and the BODIPY moiety, the quantum yield can be improved. In some embodiments, the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety may be separated by a distance of about 8 Å or greater. The linker complex maintains the distance between the blue light-absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In other embodiments, the linker complex may comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.

在一些實施例中,連接子複合物可包含視情況經取代之C 1-C 6酯基。當連接子複合物包含經取代之酯基時,連接子複合物可包括以下結構中之一者: In some embodiments, the linker complex may include optionally substituted C 1 -C 6 ester groups. When the linker complex includes a substituted ester group, the linker complex may include one of the following structures: .

在一些實施例中,連接子複合物可包含未經取代之酯基。當連接子複合物包含未經取代之酯基時,連接子複合物可包含以下結構中之一者: In some embodiments, the linker complex may include unsubstituted ester groups. When the linker complex contains an unsubstituted ester group, the linker complex may contain one of the following structures: .

在一些實施例中,連接子複合物可包含經取代之酯連接子。經取代之酯連接子可包含以下結構中之一者: 及/或 In some embodiments, the linker complex may comprise a substituted ester linker. The substituted ester linker may comprise one of the following structures: and/or .

本發明之光致發光複合物可包含BODIPY部分。BODIPY部分可具有以下通式: The photoluminescent composites of the present invention may contain a BODIPY moiety. The BODIPY part can have the following general formula: .

在一些實施例中,R 1、R 2、R 3、R 4、R 5、R 6可獨立地選自H、C 1-C 3烷基、芳基、酯或醚。在一些實施例中,R 7及R 8可獨立地選自H或甲基(-CH 3)。在一些實施例中,R 2及R 5可獨立地選自H或C 1-C 12酯。在一些實施例中,R 2及/或R 5可包含以下結構中之一者: In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 can be independently selected from H, C 1 -C 3 alkyl, aryl, ester or ether. In some embodiments, R 7 and R 8 can be independently selected from H or methyl (-CH 3 ). In some embodiments, R 2 and R 5 can be independently selected from H or C 1 -C 12 ester. In some embodiments, R 2 and/or R 5 may comprise one of the following structures: .

本發明之BODIPY部分可為如下BODIPY部分,其中R 3及R 4可各自為視情況經取代之芳基,例如苯基;R 1、R 2、R 5及R 6可獨立地為H、經取代之芳基(例如視情況經取代之苯基,諸如 )、二苯基( )及/或經C 2-C 10烷基醚取代之苯基(例如 )。 The BODIPY moiety of the present invention can be the following BODIPY moiety, wherein R 3 and R 4 can each be an optionally substituted aryl group, such as phenyl; R 1 , R 2 , R 5 and R 6 can independently be H, Substituted aryl (e.g. optionally substituted phenyl, such as ), diphenyl ( ) and/or phenyl substituted by C 2 -C 10 alkyl ether (e.g. ).

本發明之光致發光複合物可由以下結構表示,該等結構出於說明之目的提供且決不應被理解為限制性的: ,或此等結構中之任一者之組合。 The photoluminescent composites of the present invention may be represented by the following structures, which structures are provided for illustrative purposes and should in no way be construed as limiting: ; , or a combination of any of these structures.

一些實施例包括一種色轉換膜,其中該色轉換膜包含:色轉換層,其中該色轉換層包括樹脂基質及分散於該樹脂基質內的上文所描述之光致發光複合物。在一些實施例中,色轉換膜可描述為包含本文所描述之複合物中之一或多者。Some embodiments include a color conversion film, wherein the color conversion film includes: a color conversion layer, wherein the color conversion layer includes a resin matrix and the above-described photoluminescent composite dispersed within the resin matrix. In some embodiments, a color conversion film can be described as comprising one or more of the complexes described herein.

一些實施例包括可為約1 µm至約200 µm厚的色轉換膜。在一些實施例中,色轉換膜可描述為具有約1 µm至約5 µm、約5至10 µm、約10至15 µm、約15至20 µm、約20至40 µm、約40至80 µm、約80至120 µm、約120至160 µm、約160至200 µm之厚度,或由此等值中之任一者限定之範圍內的任何厚度。Some embodiments include color conversion films that may be about 1 µm to about 200 µm thick. In some embodiments, the color conversion film can be described as having about 1 µm to about 5 µm, about 5 to 10 µm, about 10 to 15 µm, about 15 to 20 µm, about 20 to 40 µm, about 40 to 80 µm , a thickness of about 80 to 120 µm, about 120 to 160 µm, about 160 to 200 µm, or any thickness within the range defined by any of these values.

在一些實施例中,色轉換膜可吸收400 nm至約480 nm波長之光且可發射約610 nm至約645 nm範圍內之光。在其他實施例中,色轉換膜可發射610 nm至約645 nm範圍內之光。In some embodiments, the color conversion film can absorb light at a wavelength of 400 nm to about 480 nm and can emit light in a range of about 610 nm to about 645 nm. In other embodiments, the color conversion film can emit light in the range of 610 nm to about 645 nm.

在一些實施例中,色轉換膜可包含透明基板層。透明基板層具有兩個相對表面,其中色轉換層可安置於透明層之將鄰近於發光源之表面上且與該等表面實體接觸。透明基板不受特別限制,且熟習此項技術者將能夠自此項技術中使用之彼等透明基板中選擇。透明基板之一些非限制性實例包括PE (聚乙烯)、PP (聚丙烯)、PEN (聚萘二甲酸乙二酯)、PC (聚碳酸酯)、PMA (聚甲基丙烯酸酯)、PMMA (聚甲基丙烯酸甲酯)、CAB (乙酸丁酸纖維素)、PVC (聚氯乙烯)、PET (聚對苯二甲酸乙二酯)、PETG (經二醇修飾之聚對苯二甲酸乙二酯)、PDMS (聚二甲基矽氧烷)、COC (環烯烴共聚物)、PGA (聚乙交酯或聚乙醇酸)、PLA (聚乳酸)、PCL (聚己內酯)、PEA (聚己二酸乙二酯)、PHA (聚羥基烷酸酯)、PHBV (聚(3-羥基丁酸酯-共聚-3-羥基戊酸酯))、PBE (聚對苯二甲酸丁二酯)、PTT (聚對苯二甲酸三亞甲基酯)、PBA (聚丙烯酸丁酯)、(丙烯酸)。適合的聚合物可為[HAB5] (Nitto Denko, Osaka, Japan)。上述樹脂中之任一者可為對應/各別單體及/或聚合物。In some embodiments, the color conversion film may include a transparent substrate layer. The transparent substrate layer has two opposite surfaces, wherein the color conversion layer can be disposed on the surface of the transparent layer that will be adjacent to the light source and in physical contact with these surfaces. The transparent substrate is not particularly limited, and those skilled in the art will be able to select from those used in the technology. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethacrylate), PMMA ( Polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (diol-modified polyethylene terephthalate) ester), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA ( Polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate) ), PTT (polytrimethylene terephthalate), PBA (polybutyl acrylate), (acrylic acid). A suitable polymer may be [HAB5] (Nitto Denko, Osaka, Japan). Any of the above resins may be corresponding/respective monomers and/or polymers.

在一些實施例中,透明基板可具有兩個相對表面。在一些實施例中,色轉換膜可安置於相對表面中之一者上且與其實體接觸。在一些實施例中,上面未安置有色轉換膜的透明基板側可鄰近於光源。在製備色轉換膜期間,基板可充當支撐件。所使用基板之類型不受特別限制,且材料及/或厚度不受限制,只要其透明且能夠充當支撐件即可。熟習此項技術者可判定使用何種材料及厚度作為支撐基板。In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film can be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate on which the colored conversion film is not disposed may be adjacent to the light source. The substrate can serve as a support during preparation of the color conversion film. The type of substrate used is not particularly limited, and the material and/or thickness are not limited as long as it is transparent and capable of acting as a support. Those skilled in the art can determine what material and thickness to use as the support substrate.

一些實施例包括一種用於製備色轉換膜之方法,其中該方法包含:將本文所描述之光致發光化合物及黏合劑樹脂溶解於溶劑內;及將混合物塗覆至透明基板之表面上。Some embodiments include a method for preparing a color conversion film, wherein the method includes: dissolving a photoluminescent compound and a binder resin described herein in a solvent; and coating the mixture onto the surface of a transparent substrate.

可與光致發光複合物一起使用之黏合劑樹脂包括樹脂,諸如丙烯酸樹脂、聚碳酸酯樹脂、乙烯-乙烯醇共聚物樹脂、乙烯-乙酸乙烯酯共聚物樹脂及其皂化產物、AS樹脂、聚酯樹脂、氯乙烯-乙酸乙烯酯共聚物樹脂、聚乙烯醇縮丁醛樹脂、聚乙烯基膦酸(PVPA)、聚苯乙烯樹脂、酚樹脂、苯氧基樹脂、聚碸、耐綸、纖維素樹脂及乙酸纖維素樹脂。在一些實施例中,黏合劑樹脂可為聚酯樹脂及/或丙烯酸樹脂。在一些實施例中,黏合劑樹脂可包含聚甲基丙烯酸酯(PMMA)。在一些實施例中,黏合劑樹脂可包含丙烯酸丁酯。在一些實施例中,黏合劑樹脂可為包含50%、75%、95%丙烯酸丁酯[共聚物]之共聚物混合物。咸信,相比於PMMA,聚(丙烯酸丁酯) (PBA)基質可提供更加非極性的環境(結構中具有正丁基烷基鏈)。咸信,PBA中之非極性環境可使得發色團染料在基質內彼此更多地聚集/堆疊,其可引起電荷轉移,因此,在PBA中通常獲得較低量子產率。Binder resins that can be used with the photoluminescent composite include resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponified products thereof, AS resins, polyethylene resins, Ester resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, polyvinylphosphonic acid (PVPA), polystyrene resin, phenol resin, phenoxy resin, polystyrene, nylon, fiber Vinegar resin and cellulose acetate resin. In some embodiments, the adhesive resin may be polyester resin and/or acrylic resin. In some embodiments, the adhesive resin may include polymethacrylate (PMMA). In some embodiments, the binder resin may include butyl acrylate. In some embodiments, the binder resin can be a copolymer mixture containing 50%, 75%, 95% butyl acrylate [copolymer]. It is believed that the poly(butyl acrylate) (PBA) matrix provides a more non-polar environment (having n-butyl alkyl chains in the structure) compared to PMMA. It is believed that the non-polar environment in PBA allows the chromophore dyes to aggregate/stack more with each other within the matrix, which can cause charge transfer and, therefore, lower quantum yields are typically obtained in PBA.

可用於溶解或分散複合物及樹脂之溶劑可包括烷烴,諸如丁烷、戊烷、己烷、庚烷及辛烷;環烷烴,諸如環戊烷、環己烷、環庚烷及環辛烷;醇,諸如乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、癸醇、十一醇、二丙酮醇及糠醇;溶纖劑(Cellosolve™),諸如甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、乙酸甲基溶纖劑及乙酸乙基溶纖劑;丙二醇及其衍生物,諸如丙二醇單甲醚、丙二醇單乙醚、丙二醇單丁醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丁醚乙酸酯及二丙二醇二甲醚;酮,諸如丙酮、甲基戊基酮、環己酮及苯乙酮;醚,諸如二㗁烷及四氫呋喃;酯,諸如乙酸丁酯、乙酸戊酯、丁酸乙酯、丁酸丁酯、草酸二乙酯、丙酮酸乙酯、2-羥基丁酸乙酯、乙醯乙酸乙酯、乳酸甲酯、乳酸乙酯及3-甲氧基丙酸甲酯;鹵化烴,諸如氯仿、二氯甲烷及四氯乙烷;芳族烴,諸如苯、甲苯、二甲苯及甲酚;及高度極性溶劑,諸如二甲基甲醯胺、二甲基乙醯胺及N-甲基吡咯啶酮。Solvents that can be used to dissolve or disperse the composites and resins may include alkanes, such as butane, pentane, hexane, heptane, and octane; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane ; Alcohols, such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol and furfuryl alcohol; Cellosolve™, such as methyl cellosolve Agent, ethyl cellosolve, butyl cellosolve, methyl acetate cellosolve and ethyl acetate cellosolve; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone and acetophenone; ethers, such as diacetyl Alkanes and tetrahydrofuran; esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetate, lactic acid Methyl ester, ethyl lactate, and methyl 3-methoxypropionate; halogenated hydrocarbons, such as chloroform, methylene chloride, and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, and cresol; and highly polar Solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

一些實施例包括一種背光單元,其中該背光單元可包括上述色轉換膜。Some embodiments include a backlight unit, wherein the backlight unit may include the color conversion film described above.

其他實施例可包括一種顯示裝置,該裝置可包含本文所描述之背光單元。Other embodiments may include a display device that may include a backlight unit as described herein.

除非另外指示,否則本說明書及實施例中所使用之表示成分量、特性(諸如分子量)、反應條件等之所有數目應理解為在所有情況下均由術語「約」修飾。因此,除非有相反指示,否則本說明書及所附實施例中所闡述之數值參數為近似值,其可視設法獲得之所需特性而變化。最低限度地,不應試圖限制等同原則之應用。在實施例之範疇內,各數值參數應至少根據所報告之有效數位之數目且藉由應用一般捨入技術來理解。Unless otherwise indicated, all numbers expressing amounts of ingredients, properties (such as molecular weight), reaction conditions, etc. used in this specification and the Examples are to be understood as modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and the accompanying examples are approximations which may vary as the desired properties are sought to be obtained. At a minimum, no attempt should be made to limit the application of the principle of equivalents. Within the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

對於所揭示之程序及/或方法,在程序及方法中執行之功能可以不同次序實施,如可能由上下文所指示。此外,所概述之步驟及操作僅作為實例提供,且一些步驟及操作可為視情況存在的,合併成較少步驟及操作,或擴展成額外步驟及操作。For the disclosed procedures and/or methods, the functions performed in the procedures and methods may be performed in a different order, as may be indicated by the context. Furthermore, the steps and operations outlined are provided as examples only, and some steps and operations may be consolidated into fewer steps and operations, or expanded into additional steps and operations, as appropriate.

本發明有時可說明包含於其他不同組件內或與其他不同組件連接的不同組件。此類所描繪架構僅為實例,且可實施達成相同或類似功能性之許多其他架構。The invention may sometimes describe different components contained within or connected to other different components. Such depicted architectures are examples only, and many other architectures may be implemented that achieve the same or similar functionality.

本發明及所附實施例(例如所附實施例之主體)中所使用之術語通常意欲作為「開放」術語(例如,術語「包括(including)」應解釋為「包括但不限於」,術語「具有」應解釋為「至少具有」,術語「包括(includes)」應解釋為「包括但不限於」等)。另外,若引入特定數目之要素,則此可解釋為意謂至少所述數目,如可由上下文所指示(例如,不具有其他修飾語的「兩個敍述物」之基本敍述意謂兩個或更多個敍述物之至少兩次敍述)。如本發明中所使用,呈現兩個或更多個替代性術語之任何分離性詞語及/或片語應理解為涵蓋包括該等術語中之一者、該等術語中之任一者或兩個術語之可能性。舉例而言,片語「A或B」:應理解為包括「A」或「B」或「A及B」的可能性。The terms used in this disclosure and the accompanying embodiments (such as the subject matter of the appended embodiments) are generally intended to be "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term " "Have" should be interpreted as "at least have", and the term "includes" should be interpreted as "including but not limited to", etc.). Additionally, if a specific number of elements is introduced, this may be interpreted to mean at least that number, as may be indicated by the context (e.g., a base recitation of "two recitals" without other modifiers means two or more At least two narrations of multiple narrative objects). As used in this invention, any discrete word and/or phrase presenting two or more alternative terms shall be understood to include the inclusion of one, either or both of those terms. the possibility of a term. For example, the phrase "A or B": should be understood to include the possibility of "A" or "B" or "A and B".

除非本文另外指示或與上下文明顯矛盾,否則在描述本發明之上下文中(尤其在以下實施例之上下文中)使用的術語「一(a)」、「一(an)」、「該(the)」及類似指示物均解釋為涵蓋單數及複數兩者。本文中所提供的任何及所有實例或代表性語言(例如「諸如」)的使用僅意欲更好地說明本發明,且並不對任何實施例的範疇造成限制。本說明書中之任何語言均不應理解為指示任何未體現之要素為實踐本發明所必需的。Unless otherwise indicated herein or clearly contradicted by context, the terms "a", "an", "the" are used in the context of describing the present invention (especially in the context of the following examples). ” and similar indicators shall be construed to cover both the singular and the plural. The use of any and all examples, or representative language (eg, "such as") provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of any embodiment. No language in the specification should be construed as indicating any non-recited element as essential to the practice of the invention.

本文中所揭示的替代要素或實施例之分組不應解釋為限制。各群組成員可個別地或以與群組之其他成員或本文中發現之其他要素的任何組合來指代及體現。預期群組中之一或多個成員可出於便利性及/或專利性的原因而包括於群組中或自群組刪除。當任何此包括或刪除發生時,本說明書被認為如所修改地含有群組,因此滿足附加實施例中所使用之所有馬庫什(Markush)群組的書面描述。Alternative elements or groupings of embodiments disclosed herein should not be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or removed from the group for convenience and/or patentability reasons. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified, thereby satisfying the written description of all Markush groups used in the additional embodiments.

本文描述某些實施例,包括本發明人已知用於實施本發明之最佳模式。當然,此等所描述實施例之變化形式在一般熟習此項技術者閱讀前述描述後將變得顯而易見。本發明人預期熟習此項技術者適當時採用此等變化,且本發明人意欲以不同於本文中特定描述之方式來實踐本發明。因此,實施例包括如適用法律所准許的實施例中所敍述之主題的所有修改及等效物。此外,除非本文另外指示或另外與上下文明顯矛盾,否則涵蓋上文所描述之要素以其所有可能變化形式之任何組合。總之,應理解,本文所揭示之實施例說明實施例之原理。可採用之其他修改在實施例之範疇內。因此,藉助於實例但非限制,可根據本文中之教示利用替代實施例。因此,實施例不限於恰好如所展示及描述之實施例。Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations to the described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect those skilled in the art to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Furthermore, any combination of the elements described above in all possible variations thereof is encompassed unless otherwise indicated herein or otherwise clearly contradicted by context. In summary, it should be understood that the embodiments disclosed herein are illustrative of principles of embodiments. Other modifications may be employed within the scope of the embodiments. Accordingly, by way of example and not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Therefore, embodiments are not limited to those exactly as shown and described.

實施例 實施例 1一種光致發光複合物,其包含: 吸收藍光之呫噸并異喹啉衍生物; 連接子複合物,其中該連接子複合物為未經取代之酯或經取代之酯;及 硼-二吡咯亞甲基(BODIPY)部分; 其中該連接子複合物共價連接該呫噸并異喹啉衍生物與該BODIPY部分,其中該呫噸并異喹啉衍生物吸收第一激發波長之光能且將能量傳遞至該BODIPY部分,其中該BODIPY部分吸收來自該呫噸并異喹啉衍生物之該能量且發射第二較高波長之光能,且其中該光致發光複合物具有大於80%之發射量子產率。 實施例 2如實施例1之光致發光複合物,其中該呫噸并異喹啉衍生物具有以下通式: ,其中R 0為鍵、H、C 1-C 4烷基或視情況經取代之芳基。 實施例 3如實施例2之光致發光複合物,其中該視情況經取代之芳基包含 實施例 4如實施例1之光致發光複合物,其中該BODIPY部分具有以下通式: 其中R 1、R 2、R 3、R 4、R 5、R 6獨立地選自鍵、H、C 1-C 3烷基、芳基、酯及/或醚;且 其中R 7及R 8可獨立地選自鍵、H或甲基(-CH 3);且 其中L 1為連接子複合物,其中該連接子複合物為未經取代之酯或經取代之酯。 實施例 5如實施例4之光致發光複合物,其中R 3及R 4可各自為芳基,例如苯基。 實施例 6如實施例5之光致發光複合物,其中該芳基可為苯基。 實施例 7如實施例6之光致發光複合物,其中該苯基包含 或二苯基( )。 實施例 8如實施例4之光致發光複合物,其中該醚可為C 2-C 10烷基醚基( )。 實施例 9如實施例4之光致發光複合物,其中R 2及R 5可各自為酯基。 實施例 10如實施例9之光致發光複合物,其中該酯基可為C 1-C 12酯( )。 實施例 11如實施例1之光致發光複合物,其中該連接子包含 實施例 12如實施例1之光致發光複合物,其中該未經取代之酯連接子包含 實施例 13如實施例1、2、3、4、5、6、7、8、9、10、11或12之光致發光複合物,其中該連接子複合物之該經取代之酯為以下結構中之一者: 實施例 14如實施例1之光致發光複合物,其中該光致發光複合物為以下結構中之一者: PLC-1 PLC-2 PLC-3 PLC-4 PLC-5 PLC-6 PLC-7 PLC-8 PLC-9 PLC-12 PLC-13 PLC-14;或其組合。 實施例 15一種色轉換膜,其包含: 透明基板層; 色轉換層,其中該色轉換層包括樹脂基質;及 至少一種光致發光複合物,其中該至少一種光致發光複合物包含分散於該樹脂基質內的如實施例1、2、3、4、5、6、7、8、9、10、11、12、13或14之光致發光化合物。 實施例 16如實施例15之色轉換膜,其中該樹脂基質包含聚丙烯酸丁酯。 實施例 17如實施例15之色轉換膜,其進一步包含單態氧淬滅劑。 實施例 18如實施例15之色轉換膜,其進一步包含自由基捕獲劑。 實施例 19如實施例15之色轉換膜,其中該膜之厚度在10 μm與200 μm之間。 實施例 20如實施例15之色轉換膜,其中該膜吸收約400 nm至約480 nm波長範圍內之光且發射575 nm至約645 nm波長範圍內之光。 實施例 21一種用於製備色轉換膜之方法,該方法包含: 將如實施例1、2、3、4、5、6、7、8、9、10、11、12、13或14之光致發光複合物及黏合劑樹脂溶解於溶劑內;及 將該混合物塗覆至透明基板相對表面中之一者。 實施例 22如實施例21之方法,其中該黏合劑樹脂包含聚丙烯酸丁酯(HAB5)。 實施例 23一種背光單元,其包含如實施例15、16、17、18、19或20之色轉換膜。 實施例 24一種顯示裝置,其包含如實施例23之背光單元。 Examples Example 1 A photoluminescent complex, which includes: a xanthenoisoquinoline derivative that absorbs blue light; a linker complex, wherein the linker complex is an unsubstituted ester or a substituted ester; and a boron-dipyrromethene (BODIPY) moiety; wherein the linker complex covalently connects the xanthenoisoquinoline derivative to the BODIPY moiety, wherein the xanthenoisoquinoline derivative absorbs the first excitation wavelength of light energy and transfers energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the xanthenoisoquinoline derivative and emits light energy of a second higher wavelength, and wherein the photoluminescent composite Has an emission quantum yield greater than 80%. Embodiment 2 The photoluminescent composite of Embodiment 1, wherein the xanthenoisoquinoline derivative has the following general formula: , where R 0 is a bond, H, C 1 -C 4 alkyl, or optionally substituted aryl. Embodiment 3 The photoluminescent composite of Embodiment 2, wherein the optionally substituted aryl group comprises , or . Embodiment 4 The photoluminescent composite of Embodiment 1, wherein the BODIPY part has the following general formula: wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently selected from bond, H, C 1 -C 3 alkyl, aryl, ester and/or ether; and wherein R 7 and R 8 Can be independently selected from bond, H or methyl ( -CH3 ); and wherein L1 is a linker complex, wherein the linker complex is an unsubstituted ester or a substituted ester. Embodiment 5 is the photoluminescent composite of Embodiment 4, wherein R 3 and R 4 can each be an aryl group, such as phenyl. Embodiment 6 is the photoluminescent composite of Embodiment 5, wherein the aryl group can be phenyl. Embodiment 7 The photoluminescent composite of embodiment 6, wherein the phenyl group comprises or diphenyl( ). Embodiment 8 The photoluminescent composite of Embodiment 4, wherein the ether can be a C 2 -C 10 alkyl ether group ( ). Embodiment 9 is the photoluminescent composite of Embodiment 4, wherein R 2 and R 5 can each be an ester group. Embodiment 10 The photoluminescent composite of Embodiment 9, wherein the ester group can be C 1 -C 12 ester ( ). Embodiment 11 The photoluminescent complex of embodiment 1, wherein the linker comprises . Embodiment 12 The photoluminescent composite of embodiment 1, wherein the unsubstituted ester linker comprises . Embodiment 13 The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein the substituted ester of the linker complex is as follows One of the structures: . Embodiment 14 The photoluminescent composite of Embodiment 1, wherein the photoluminescent composite is one of the following structures: PLC-1 PLC-2 PLC-3 PLC-4 PLC-5 PLC-6 PLC-7 PLC-8 PLC-9 , ; ; PLC-12 ; PLC-13 ; PLC-14 ; or combination thereof. Embodiment 15 A color conversion film, comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix; and at least one photoluminescent compound, wherein the at least one photoluminescent compound includes dispersed in the The photoluminescent compound of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 within a resin matrix. Embodiment 16 is the color conversion film of embodiment 15, wherein the resin matrix includes polybutyl acrylate. Embodiment 17 is the color conversion film of Embodiment 15, further comprising a singlet oxygen quencher. Embodiment 18 is the color conversion film of Embodiment 15, further comprising a radical scavenger. Embodiment 19 The color conversion film of Embodiment 15, wherein the thickness of the film is between 10 μm and 200 μm. Embodiment 20 is the color conversion film of Embodiment 15, wherein the film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of 575 nm to about 645 nm. Embodiment 21 A method for preparing a color conversion film, the method comprising: using light as in embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 The luminescent compound and the binder resin are dissolved in a solvent; and the mixture is coated on one of the opposite surfaces of the transparent substrate. Embodiment 22 is the method of embodiment 21, wherein the adhesive resin includes polybutyl acrylate (HAB5). Embodiment 23 is a backlight unit, which includes the color conversion film of Embodiment 15, 16, 17, 18, 19 or 20. Embodiment 24 is a display device, which includes the backlight unit of Embodiment 23.

實例已發現,相較於用於色轉換膜之其他形式之染料,本文所描述之光致發光複合物之實施例具有改良之效能。此等益處由以下實例進一步證實,該等實例僅意欲說明本發明,但並不意欲以任何方式限制範疇或基礎原理。 EXAMPLES Embodiments of the photoluminescent composites described herein have been found to have improved performance compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are merely intended to illustrate the invention but are not intended to limit the scope or underlying principles in any way.

實例 1.1 比較實例 1 (CE-1) Example 1.1 compared to Example 1 (CE-1) :

CE-1:將0.75 g 4-羥基-2,6-二甲基苯甲醛(5 mmol)及1.04 g 2,4-二甲基吡咯(11 mmol)溶解於100 mL無水二氯甲烷中。使溶液脫氣30分鐘。隨後添加一滴三氟乙酸。將溶液在氬氣氛圍下在室溫下攪拌過夜。向所得溶液中添加DDQ (2,3-二氯-5,6-二氰基-1,4-苯醌) (2.0 g),且將混合物攪拌過夜。第二天,過濾溶液,且隨後用二氯甲烷洗滌,得到二吡咯甲烷(1.9 g)。隨後,將1.0 g二吡咯甲烷溶解於60 mL THF中。將5 mL三甲胺添加至溶液中,且隨後脫氣10分鐘。在脫氣之後,緩慢添加5 mL三氟化硼-二乙醚,接著在70℃下加熱30分鐘。將所得溶液負載於矽膠上,且藉由急驟層析使用二氯甲烷作為溶離劑來純化。收集所需溶離份且減壓乾燥,得到0.9 g或橙色固體(76%產率)。LCMS (APCI+):C 21H 24BF 2N 2O (M+H)之計算值 = 369;實驗值:369。1H NMR (400 MHz, 氯仿-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H)。 CE-1: Dissolve 0.75 g 4-hydroxy-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g 2,4-dimethylpyrrole (11 mmol) in 100 mL anhydrous dichloromethane. Degas the solution for 30 minutes. Then add a drop of trifluoroacetic acid. The solution was stirred overnight at room temperature under an argon atmosphere. To the resulting solution, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (2.0 g) was added, and the mixture was stirred overnight. The next day, the solution was filtered and subsequently washed with dichloromethane to give dipyrromethane (1.9 g). Subsequently, 1.0 g of dipyrromethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of boron trifluoride-diethyl ether was slowly added, followed by heating at 70°C for 30 minutes. The resulting solution was loaded on silica gel and purified by flash chromatography using dichloromethane as the eluent. The required fractions were collected and dried under reduced pressure to obtain 0.9 g or orange solid (76% yield). LCMS (APCI+): Calculated for C 21 H 24 BF 2 N 2 O (M+H) = 369; found: 369. 1H NMR (400 MHz, chloroform-d) δ 6.64 (s, 2H), 5.97 ( s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).

實例 1.2 比較實例 2 (CE-2) 比較實例 2Wakamiya, Atsushi 等人 Chemistry Letters, 37(10), 1094-1095; 2008中所描述合成。 Example 1.2 Comparative Example 2 (CE-2) : Comparative Example 2 was synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008 .

實例 2 光致發光複合物之合成 化合物 PLC-1 之合成 Example 2 Synthesis of Photoluminescent Complex : Synthesis of Compound PLC-1

化合物 PLC-1.1:使4-溴-1,8-萘二甲酸酐(2.77 g,10 mmol)、4-溴-2-硝基苯酚(3.27 g,15 mmol)之混合物真空脫氣30分鐘,隨後添加無水NMP (50 mL),接著添加氫氧化鈉(0.2 g,5 mmol)及銅粉(0.318 g,5 mmol)。將混合物用氬氣鼓泡20分鐘,隨後在氬氣氛圍下在180℃下加熱過夜。在冷卻至室溫之後,向溶液中逐滴添加50 mL 20%鹽酸水溶液,隨後添加50 mL水。使所得混合物靜置3小時,隨後過濾以收集沈澱物,真空乾燥,得到4.6 g粗產物。將粗產物分散於30 mL丙酮中且在室溫下攪拌過夜以溶解雜質。過濾且真空乾燥,得到作為所需產物之棕黃色固體(3.3 g,80%產率)。LCMS (APCI+):C 18H 9BrNO 6(M+H)之計算值 = 413.95;實驗值:414。1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H)。 Compound PLC-1.1 : The mixture of 4-bromo-1,8-naphthalenedicarboxylic anhydride (2.77 g, 10 mmol) and 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was vacuum degassed for 30 minutes. Anhydrous NMP (50 mL) was then added, followed by sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was bubbled with argon for 20 minutes and then heated at 180°C overnight under an argon atmosphere. After cooling to room temperature, 50 mL of 20% aqueous hydrochloric acid solution was added dropwise to the solution, followed by 50 mL of water. The resulting mixture was allowed to stand for 3 hours, then filtered to collect the precipitate and dried under vacuum to obtain 4.6 g of crude product. The crude product was dispersed in 30 mL acetone and stirred at room temperature overnight to dissolve impurities. Filtration and drying under vacuum gave the desired product as a tan solid (3.3 g, 80% yield). LCMS (APCI+): Calculated for C 18 H 9 BrNO 6 (M+H) = 413.95; Found: 414. 1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H ), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H).

化合物 PLC-1.2:將 PLC-1.1(1.5 g,3.6 mmol)、鐵粉(0.60 g,10.8 mmol)於乙酸(50 mL)中之混合物在125℃下加熱30分鐘。在冷卻至室溫之後,向混合物中添加100 mL水,同時攪拌。過濾所得混合物且用水洗滌,在空氣及真空中乾燥,得到固體(1.35 g,82%產率)。LCMS (APCI-):C 18H 10BrNO 4之計算值 = 382.98;實驗值:383。1H NMR (400 MHz, DMSO-d6) δ 9.01 - 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H)。 Compound PLC-1.2 : A mixture of PLC-1.1 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125°C for 30 minutes. After cooling to room temperature, 100 mL of water was added to the mixture while stirring. The resulting mixture was filtered and washed with water, dried in air and under vacuum to give a solid (1.35 g, 82% yield). LCMS (APCI-): Calculated for C 18 H 10 BrNO 4 = 382.98; Found: 383. 1H NMR (400 MHz, DMSO-d6) δ 9.01 - 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H).

化合物 PLC-1.3:將 PLC-1.2(2.65 g,6.9 mmol)分散於乙酸(50 mL)/水(10 mL)中且冷卻至0℃。在攪拌的同時,添加預冷卻之鹽酸(2.8 mL,34.5 mmol),隨後在0℃下逐滴添加亞硝酸鈉(3.57 g,52 mmol)於15 mL水中之溶液。將整體在0℃下攪拌一小時,隨後轉移至另一漏斗中,且在130℃下經一小時時段滴入硫酸銅溶液(12 g,47 mmol,於140 mL水中)中。在冷卻至室溫之後,藉由過濾收集沈澱物,用水(100 mL × 3)洗滌,隨後在40℃下在50 mL丙酮中攪拌30分鐘。過濾,在空氣中隨後在真空中乾燥,得到棕黃色固體(1.76 g,70%產率)。LCMS (APCI+):C 18H 8BrO 4(M+H)之計算值 = 366.95;實驗值:367。1H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H)。] Compound PLC-1.3 : PLC-1.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL)/water (10 mL) and cooled to 0°C. While stirring, precooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, followed by a solution of sodium nitrite (3.57 g, 52 mmol) in 15 mL of water dropwise at 0°C. The whole was stirred at 0°C for one hour, then transferred to another funnel and copper sulfate solution (12 g, 47 mmol in 140 mL water) dropped at 130°C over a period of one hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL × 3), and then stirred in 50 mL acetone at 40°C for 30 min. Filtration, drying in air and then in vacuo gave a tan solid (1.76 g, 70% yield). LCMS (APCI+): Calcd. for C 18 H 8 BrO 4 (M+H) = 366.95; found: 367. 1H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H ), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H ), 7.23 (d, J = 8.8 Hz, 1H). ]

化合物 PLC-1.4:2-(4-(9-溴-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸:在室溫下使 PLC-1.3(400.0 mg,1.1 mmol)、4-胺基苯基乙酸(329.4 mg,2.2 mmol)及DMAP (9.3 mg,0.080 mmol)於DMF (8 mL)中之混合物脫氣。隨後將混合物加熱至165℃且保持在此溫度下3小時。TLC及LCMS顯示約95%轉化率,無可觀測副反應。將混合物冷卻至50℃。隨後將其傾入已藉由水-冰浴預先冷卻之丙酮溶液(40 mL)中。將混合物保持在0℃下2小時,且隨後在室溫下保持攪拌過夜。經由真空過濾收集固體且藉由丙酮(4 mL)洗滌。且藉由真空烘箱在100℃下乾燥3小時,得到呈黃棕色固體狀之純化合物 PLC-1.4(395.0 mg,73%產率)。MS (APCI):化學式:C 26H 14BrNO 5([M+H]+)之計算值 = 500,實驗值:500。1H NMR (400 MHz, CDCl2CDCl2) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H)。 Compound PLC-1.4 : 2-(4-(9-bromo-1,3-bisoxy-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)benzene Acetic acid: PLC-1.3 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) at room temperature. The mixture is degassed. The mixture was then heated to 165°C and maintained at this temperature for 3 hours. TLC and LCMS showed about 95% conversion rate and no observable side reactions. The mixture was cooled to 50°C. This was then poured into an acetone solution (40 mL) that had been pre-cooled by a water-ice bath. The mixture was kept at 0°C for 2 hours and then kept stirring at room temperature overnight. The solid was collected via vacuum filtration and washed with acetone (4 mL). And by drying in a vacuum oven at 100°C for 3 hours, pure compound PLC-1.4 (395.0 mg, 73% yield) was obtained as a yellow-brown solid. MS (APCI): Chemical formula: Calculated value of C 26 H 14 BrNO 5 ([M+H]+) = 500, experimental value: 500. 1H NMR (400 MHz, CDCl2CDCl2) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H ).

化合物 PLC-1.5:2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸:100 mL小瓶裝配有攪拌棒。在小瓶中,在室溫下使含 PLC-1.4(400.0 mg,0.80 mmol)、4-(三氟甲基)苯基硼酸(262.2 mg,1.6 mmol)、Pd(dppf)Cl 2(41.0 mg,0.056 mmol)及K 2CO 3(298.0 mg,2.2 mmol)之THF/DMF/H 2O (22 mL/4.4 mL/2.2 mL)脫氣。將反應混合物加熱至80℃且將反應物保持在此溫度下過夜。TLC用於監測反應。完成後,藉由添加0.1 N HCl (150 mL)及EtOAc (150 mL)來處理反應物。藉由THF (150 mL×3)進一步萃取水相。合併之有機相經無水Na 2SO 4乾燥,在旋轉蒸發儀下濃縮,且藉由急驟層析使用DCM/EtOAc (0-40%,含0.1% TFA)作為溶離劑來純化,得到呈黃色/黃棕色固體狀之純 PLC-1.5。363.0 mg,80%產率。MS (APCI):化學式:C 33H 18F 3NO 5([M+H]+)之計算值 = 566,實驗值:566。1H NMR (400 MHz, DMSO-d6) 8.76 (m, 1H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H)。 Compound PLC-1.5 : 2-(4-(1,3-bisoxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def]iso Quinolin-2(3H)-yl)phenyl)acetic acid: 100 mL vial equipped with stir bar. In a vial, mix PLC-1.4 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl 2 (41.0 mg, Degas 0.056 mmol) and K 2 CO 3 (298.0 mg, 2.2 mmol) in THF/DMF/H 2 O (22 mL/4.4 mL/2.2 mL). The reaction mixture was heated to 80°C and the reaction was maintained at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was treated by adding 0.1 N HCl (150 mL) and EtOAc (150 mL). The aqueous phase was further extracted with THF (150 mL×3). The combined organic phases were dried over anhydrous Na 2 SO 4 , concentrated on a rotary evaporator, and purified by flash chromatography using DCM/EtOAc (0-40%, containing 0.1% TFA) as the eluent to obtain a yellow/ Pure PLC-1.5 in yellow-brown solid form. 363.0 mg, 80% yield. MS (APCI): Chemical formula: Calculated value for C 33 H 18 F 3 NO 5 ([M+H]+) = 566, found value: 566. 1H NMR (400 MHz, DMSO-d6) 8.76 (m, 1H) , 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H) , 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H).

化合物 PLC-1.6 步驟1:將2-(4-溴苯基)-4-苯基-1H-吡咯( PLC-1.2) (1.0 g,3.36 mmol)、4-羥基-2,6-二甲基苯甲醛(0.252 g,1.68 mmol)及p-TsOH (50 mg)於1,2-二氯乙烷(50 mL)中之混合物在60℃下加熱48小時。LCMS分析顯示主峰為所需產物,其中m/e+ = 727。 Compound PLC-1.6 : Step 1: Combine 2-(4-bromophenyl)-4-phenyl-1H-pyrrole ( PLC-1.2 ) (1.0 g, 3.36 mmol), 4-hydroxy-2,6-dimethyl A mixture of p-TsOH (0.252 g, 1.68 mmol) and p-TsOH (50 mg) in 1,2-dichloroethane (50 mL) was heated at 60°C for 48 hours. LCMS analysis showed that the main peak was the desired product with m/e+ = 727.

步驟2:向來自步驟1之混合物中添加DDQ (2,3-二氯-5,6-二氰基-1,4-苯醌) (570 mg,2.51 mmol),且在室溫下攪拌30分鐘。LCMS分析顯示反應完成,其中m/e-之主峰 = 723。Step 2: Add DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (570 mg, 2.51 mmol) to the mixture from step 1 and stir at room temperature for 30 minute. LCMS analysis showed the reaction was complete with m/e-main peak = 723.

步驟3:在0℃下向來自步驟2之混合物中添加三乙胺(1.7 mL,12 mmol)、三氟化硼二乙醚(BF 3•OEt 2) (3.5 mL,28 mmol)。將整體在50℃下加熱一小時。LCMS顯示反應完成,其中m/e-之主峰 = 772。混合物用100 mL二氯甲烷(DCM)稀釋,隨後用水洗滌兩次,用鹽水洗滌一次,隨後負載至矽膠上,藉由急驟層析使用溶離劑己烷/DCM (0%至100% DCM)純化。收集第2主要所需峰,減壓移除溶劑之後,獲得呈紫色固體狀之所需產物(0.45 g,34.6%產率)。藉由LCMS (APCI)確認:C 41H 29BBr 2F 2N 2O (M-)之計算值:772.07;實驗值:772。1H NMR (400 MHz, d2-TCE) δ 7.84 - 7.64 (m, 4H), 7.61 - 7.42 (m, 4H), 7.03 - 6.81 (m, 6H), 6.77 - 6.64 (m, 4H), 6.38 (s, 2H), 5.62 (s, 2H), 1.89 (s, 6H)。 Step 3: To the mixture from step 2, add triethylamine (1.7 mL, 12 mmol), boron trifluoride diethyl ether (BF 3 •OEt 2 ) (3.5 mL, 28 mmol) at 0°C. The whole was heated at 50°C for one hour. LCMS showed the reaction was complete with m/e-main peak = 772. The mixture was diluted with 100 mL dichloromethane (DCM), washed twice with water and once with brine, then loaded onto silica gel and purified by flash chromatography using the eluant hexane/DCM (0% to 100% DCM) . The second main desired peak was collected, and after removing the solvent under reduced pressure, the desired product was obtained as a purple solid (0.45 g, 34.6% yield). Confirmed by LCMS (APCI): Calculated for C 41 H 29 BBr 2 F 2 N 2 O (M-): 772.07; Found: 772. 1H NMR (400 MHz, d2-TCE) δ 7.84 - 7.64 (m , 4H), 7.61 - 7.42 (m, 4H), 7.03 - 6.81 (m, 6H), 6.77 - 6.64 (m, 4H), 6.38 (s, 2H), 5.62 (s, 2H), 1.89 (s, 6H ).

化合物 PLC-1:將 PLC-1.6(50 mg,0.0645 mmol)、2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸(50 mg,0.089 mmol)、DIC (0.15 mL,0.945 mmol)、DMAP/p-TsOH (50 mg,0.17 mmol)於DCM (5 mL)中之混合物在室溫下攪拌過夜,隨後用20 mL DCM稀釋且負載於矽膠上,並且藉由急驟層析使用溶離劑己烷/DCM (0%至100% DCM)來純化。收集主要所需溶離份。減壓移除溶劑,用甲醇濕磨並過濾,得到深紫色固體(40 mg,47%產率)。LCMS (APCI-):C 74H 45BBr 2F 5N 3O 5之計算值:1319.19;實驗值:1319。1H NMR (400 MHz, d2-TCE) δ 8.59 (dd, J = 19.2, 8.1 Hz, 2H), 8.21 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.78 - 7.67 (m, 9H), 7.57 - 7.43 (m, 7H), 7.32 (dd, J = 17.5, 8.3 Hz, 3H), 7.00 - 6.85 (m, 6H), 6.74 - 6.63 (m, 4H), 6.38 (s, 2H), 6.02 (s, 2H), 3.81 (s, 2H), 1.96 (s, 6H)。 Compound PLC-1 : PLC-1.6 (50 mg, 0.0645 mmol), 2-(4-(1,3-bisoxy-9-(4-(trifluoromethyl)phenyl))-1H-x Anto[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (50 mg, 0.089 mmol), DIC (0.15 mL, 0.945 mmol), DMAP/p-TsOH (50 mg, 0.17 mmol) in DCM (5 mL) was stirred at room temperature overnight, then diluted with 20 mL DCM and loaded on silica gel and subjected to flash chromatography using the eluent hexane/DCM (0% to 100% DCM) for purification. Collect the main required fractions. The solvent was removed under reduced pressure, triturated with methanol and filtered to obtain a dark purple solid (40 mg, 47% yield). LCMS (APCI-): Calculated for C 74 H 45 BBr 2 F 5 N 3 O 5 : 1319.19; Found: 1319. 1H NMR (400 MHz, d2-TCE) δ 8.59 (dd, J = 19.2, 8.1 Hz , 2H), 8.21 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.78 - 7.67 (m, 9H), 7.57 - 7.43 (m, 7H), 7.32 (dd, J = 17.5, 8.3 Hz, 3H), 7.00 - 6.85 (m, 6H), 6.74 - 6.63 (m, 4H), 6.38 (s, 2H), 6.02 (s, 2H), 3.81 (s, 2H), 1.96 (s, 6H).

化合物 PLC-3 之合成 Synthesis of compound PLC-3

化合物 PLC-3.4:將 PLC-1.3(550 mg,1.5 mmol)、4-(4-胺基苯基)丁酸(537 mg,3 mmol)及DMAP (12.2 mg,0.1 mmol)於10 mL DMF中之混合物在微波反應器中在165℃下加熱2.5小時。在攪拌的同時將所得溶液滴入50 mL丙酮中。形成沈澱物並過濾,且在60℃下在真空烘箱中乾燥過夜,得到呈棕黃色固體狀之所需產物(0.49 g,62%產率)。LCMS (APCI-):C 28H 18BrNO 5之計算值 = 527.04;實驗值:527。1H NMR (400 MHz, DMSO-d6) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 - 2.55 (m, 2H), 2.27 - 2.15 (m, 2H), 1.87 - 1.73 (m, 2H)。 Compound PLC-3.4 : Dissolve PLC-1.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butyric acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) in 10 mL DMF The mixture was heated in a microwave reactor at 165°C for 2.5 hours. The resulting solution was dropped into 50 mL of acetone while stirring. A precipitate formed and was filtered and dried in a vacuum oven at 60°C overnight to give the desired product as a tan solid (0.49 g, 62% yield). LCMS (APCI-): Calculated for C 28 H 18 BrNO 5 = 527.04; Found: 527. 1H NMR (400 MHz, DMSO-d6) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 - 2.55 (m, 2H), 2.27 - 2.15 (m, 2H), 1.87 - 1.73 (m, 2H) .

化合物 PLC-3.5:使 PLC-3.4(649 mg,1.23 mmol)、4-(三氟甲基)苯基硼酸(467 mg,2.46 mmol)、Pd(dppf)Cl 2(45 mg,0.06 mmol)、碳酸鉀(345 mg,2.5 mmol)於THF/DMF/水(30 mL/6 mL/3 mL)之共溶劑中之混合物脫氣,隨後在80℃下加熱過夜。用300 mL乙酸乙酯及50 mL 0.6 N鹽酸水溶液處理混合物。用乙酸乙酯(150 mL × 3)萃取水相。收集有機相且用鹽水(100 mL × 2)洗滌,經硫酸鈉乾燥,隨後乾燥負載於矽膠上且藉由急驟層析使用溶離劑DCM/EA (0%至80% EA,含0.1% TFA)純化。收集主要所需溶離份,減壓移除溶劑,得到黃色固體(414 mg,57%產率)。1H NMR (400 MHz, d2-TCE) δ 8.55 (dd, J = 18.1, 8.1 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.43 (d, J = 8.6 Hz, 1H), 7.32 (tt, J = 8.2, 4.2 Hz, 5H), 7.20 - 7.13 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.4 Hz, 2H)。 Compound PLC-3.5 : PLC-3.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), Pd(dppf)Cl 2 (45 mg, 0.06 mmol), A mixture of potassium carbonate (345 mg, 2.5 mmol) in a co-solvent of THF/DMF/water (30 mL/6 mL/3 mL) was degassed and then heated at 80°C overnight. The mixture was treated with 300 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. Extract the aqueous phase with ethyl acetate (150 mL × 3). The organic phase was collected and washed with brine (100 mL × 2), dried over sodium sulfate, and then dried and loaded on silica gel and subjected to flash chromatography using the eluent DCM/EA (0% to 80% EA, containing 0.1% TFA) Purification. The main desired fractions were collected, and the solvent was removed under reduced pressure to obtain a yellow solid (414 mg, 57% yield). 1H NMR (400 MHz, d2-TCE) δ 8.55 (dd, J = 18.1, 8.1 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.43 (d, J = 8.6 Hz, 1H), 7.32 (tt, J = 8.2, 4.2 Hz, 5H), 7.20 - 7.13 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.4 Hz, 2H).

化合物 PLC-3:將 PLC-1.6(77.5 mg,0.1 mmol)、4-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)丁酸(100 mg,0.17 mmol)、DIC (0.1 mL,0.63 mmol)、DMAP/p-TsOH (29 mg,0.1 mmol)於DCM (8 mL)中之混合物在室溫下攪拌過夜,隨後用10 mL DCM稀釋且負載於矽膠上,並且藉由急驟層析使用溶離劑DCM/EA (0%至5% EA)來純化。收集主要所需溶離份,減壓濃縮,用甲醇濕磨並過濾,得到深紅色固體(90 mg,67%產率)。LCMS (APCI-):C 76H 49BBr 2F 5N 3O 5之計算值:1347.21;實驗值:1347。1H NMR (400 MHz, d2-TCE) δ 8.57 (dd, J = 18.8, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.72 (dt, J = 8.6, 2.7 Hz, 9H), 7.57 - 7.49 (m, 4H), 7.46 (d, J = 8.6 Hz, 1H), 7.41 - 7.36 (m, 2H), 7.33 (d, J = 8.3 Hz, 1H), 7.26 - 7.17 (m, 2H), 7.02 - 6.84 (m, 6H), 6.68 (dt, J = 6.9, 1.4 Hz, 4H), 6.38 (s, 2H), 5.99 (s, 2H), 2.76 (t, J = 7.5 Hz, 2H), 2.47 (t, J = 7.4 Hz, 2H), 2.05 (p, J = 7.5 Hz, 2H), 1.96 (s, 6H)。 Compound PLC-3 : PLC-1.6 (77.5 mg, 0.1 mmol), 4-(4-(1,3-bisoxy-9-(4-(trifluoromethyl)phenyl))-1H-x Anto[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butyrate (100 mg, 0.17 mmol), DIC (0.1 mL, 0.63 mmol), DMAP/p-TsOH ( A mixture of 29 mg, 0.1 mmol) in DCM (8 mL) was stirred at room temperature overnight, then diluted with 10 mL DCM and loaded on silica gel and subjected to flash chromatography using the eluent DCM/EA (0% to 5% EA) for purification. The main required eluate fractions were collected, concentrated under reduced pressure, wet-triturated with methanol and filtered to obtain a dark red solid (90 mg, 67% yield). LCMS (APCI-): Calculated for C 76 H 49 BBr 2 F 5 N 3 O 5 : 1347.21; Found: 1347. 1H NMR (400 MHz, d2-TCE) δ 8.57 (dd, J = 18.8, 8.1 Hz , 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.72 (dt, J = 8.6, 2.7 Hz, 9H), 7.57 - 7.49 (m, 4H) , 7.46 (d, J = 8.6 Hz, 1H), 7.41 - 7.36 (m, 2H), 7.33 (d, J = 8.3 Hz, 1H), 7.26 - 7.17 (m, 2H), 7.02 - 6.84 (m, 6H ), 6.68 (dt, J = 6.9, 1.4 Hz, 4H), 6.38 (s, 2H), 5.99 (s, 2H), 2.76 (t, J = 7.5 Hz, 2H), 2.47 (t, J = 7.4 Hz , 2H), 2.05 (p, J = 7.5 Hz, 2H), 1.96 (s, 6H).

化合物 PLC-4 之合成 Synthesis of compound PLC-4

化合物 PLC-4.1 ((E)-1-(4-(三級丁基)苯基)-3-苯基丙-2-烯-1-酮):向100 mL回收燒瓶中裝入攪拌棒。向燒瓶中添加1-(4-(三級丁基)苯基)乙-1-酮(10.0 mmol,1.83 mL)、苯甲醛(10.0 mmol,1.00 mL)及200標準酒精度(proof)之乙醇(5 mL)。在室溫下攪拌混合物且添加水(2.4 mL),接著經45秒逐滴添加5 M KOH (12.00 mmol,2.4 mL)。將反應物在室溫下劇烈攪拌6小時。用水(50 mL)稀釋反應混合物且攪拌10分鐘。濾出沈澱物,用水洗滌。藉由抽吸乾燥,隨後溶解於DCM中且在真空中蒸發至乾燥。得到2.386 g灰白色固體(90%產率)。MS (APCI):化學式:C 19H 20O (M+H)之計算值 = 265;實驗值:265。1H NMR (400 MHz, TCE) δ 8.01 - 7.95 (m, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.70 - 7.64 (m, 2H), 7.57 (d, J = 11.0 Hz, 1H), 7.55 - 7.52 (m, 2H), 7.49 - 7.43 (m, 3H), 1.37 (s, 9H)。 Compound PLC-4.1 : (( E)-1-(4-(tertiary butyl)phenyl)-3-phenylprop-2-en-1-one): Add a stirring rod to the 100 mL recovery flask . Add 1-(4-(tertiary butyl)phenyl)ethan-1-one (10.0 mmol, 1.83 mL), benzaldehyde (10.0 mmol, 1.00 mL) and 200 proof ethanol to the flask. (5 mL). The mixture was stirred at room temperature and water (2.4 mL) was added, followed by 5 M KOH (12.00 mmol, 2.4 mL) dropwise over 45 seconds. The reaction was stirred vigorously at room temperature for 6 hours. The reaction mixture was diluted with water (50 mL) and stirred for 10 minutes. The precipitate was filtered off and washed with water. Dry by suction, then dissolve in DCM and evaporate to dryness in vacuo. 2.386 g of off-white solid were obtained (90% yield). MS (APCI): Chemical formula: Calculated value for C 19 H 20 O (M+H) = 265; found value: 265. 1H NMR (400 MHz, TCE) δ 8.01 - 7.95 (m, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.70 - 7.64 (m, 2H), 7.57 (d, J = 11.0 Hz, 1H), 7.55 - 7.52 (m, 2H), 7.49 - 7.43 (m, 3H), 1.37 (s , 9H).

化合物 PLC-4.2 (1-(4-(三級丁基)苯基)-4-硝基-3-苯基丁-1-酮):以與 PLC-2.2(見下文)類似之方式,在95℃下在200標準酒精度之乙醇(11 mL)及硝基甲烷(11 mL)中由化合物 PLC-4.1(9.018 mmol,2.384 g)及KOH (1.804 mmol,101 mg)合成化合物 PLC-4.2,持續一小時。將粗反應混合物分配於水(100 mL)與EtOAc (100 mL)之間。添加少量NaCl以破壞乳液。有機層經MgSO 4乾燥,過濾,且在真空中蒸發至乾燥。得到2.784 g棕色油狀物(95%產率)。MS (APCI):化學式:C 20H 23NO 3(M+H)之計算值 = 326;實驗值:326。1H NMR (400 MHz, TCE) δ 7.90 - 7.83 (m, 2H), 7.52 - 7.46 (m, 2H), 7.40 - 7.34 (m, 2H), 7.34 - 7.26 (m, 3H), 4.85 (dd, J = 12.5, 6.3 Hz, 1H), 4.69 (dd, J = 12.5, 8.3 Hz, 1H), 4.21 (tt, J = 8.1, 6.2 Hz, 1H), 3.47 (dd, J = 17.8, 6.1 Hz, 1H), 3.39 (dd, J = 17.8, 7.8 Hz, 1H), 1.34 (s, 9H)。 Compound PLC-4.2 : (1-(4-(tertiary butyl)phenyl)-4-nitro-3-phenylbutan-1-one): In a similar manner to PLC-2.2 (see below), Compound PLC-4.2 was synthesized from compound PLC-4.1 (9.018 mmol, 2.384 g) and KOH (1.804 mmol, 101 mg) in 200 standard alcohol ethanol (11 mL) and nitromethane (11 mL) at 95°C. , lasts one hour. The crude reaction mixture was partitioned between water (100 mL) and EtOAc (100 mL). Add a small amount of NaCl to break the emulsion. The organic layer was dried over MgSO4 , filtered, and evaporated in vacuo to dryness. 2.784 g of brown oil were obtained (95% yield). MS (APCI): Chemical formula: Calculated value for C 20 H 23 NO 3 (M+H) = 326; found value: 326. 1H NMR (400 MHz, TCE) δ 7.90 - 7.83 (m, 2H), 7.52 - 7.46 (m, 2H), 7.40 - 7.34 (m, 2H), 7.34 - 7.26 (m, 3H), 4.85 (dd, J = 12.5, 6.3 Hz, 1H), 4.69 (dd, J = 12.5, 8.3 Hz, 1H ), 4.21 (tt, J = 8.1, 6.2 Hz, 1H), 3.47 (dd, J = 17.8, 6.1 Hz, 1H), 3.39 (dd, J = 17.8, 7.8 Hz, 1H), 1.34 (s, 9H) .

化合物 PLC-4.4 (2-(4-(三級丁基)苯基)-4-苯基-1H-吡咯): 用含KOH (17.66 mmol,991 mg)之無水THF (75 mL)及無水MeOH (40 mL)處理 PLC-4.2(6.822 mmol,2.220 g),隨後將此溶液滴入無水甲醇(40 mL)及96% H 2SO 4(8.5 mL)之冰冷混合物中。在添加之後,使反應物升溫至室溫。將反應物在室溫下再保持1小時。LCMS顯示反應完成。將反應溶液傾入碎冰中且用EtOAc (150 ml ×3)萃取。合併之有機相用含10% (w/w) Na 2CO 3之H 2O且隨後用鹽水洗滌。經無水Na 2SO 4乾燥之後,在真空旋轉蒸發儀下濃縮溶液,得到呈油狀物之所需產物 PLC-4.3,其不經進一步純化即用於下一步驟。粗產物藉由LCMS及NMR驗證為二甲基縮醛。將粗縮醛溶解於乙酸(15 mL)中且用乙酸銨(33.155 mmol)處理。在100℃下加熱過夜之後,將反應混合物冷卻至室溫且添加水。濾出所得沈澱物,將其溶解於DCM中,經MgSO 4乾燥。將粗沈澱物蒸發至約20 g矽膠上,且將此矽膠置於負載器中。藉由急驟層析在矽膠(120 g,固體負載,平衡20% EtOAc/己烷,溶離0% (2 CV)至20% EtOAc/己烷(15 CV))上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到1452 mg呈淡藍紫色固體狀之所需產物 PLC-4.4(自化合物PLC 4.2之產率77.3%)。MS (APCI):化學式:C 20H 21N (M+H)之計算值 = 276;實驗值:276。1H NMR (400 MHz, TCE) δ 8.51 (s, 1H), 7.63 - 7.55 (m, 2H), 7.50 - 7.41 (m, 4H), 7.38 (t, J = 7.7 Hz, 2H), 7.26 - 7.19 (m, 1H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.80 (dd, J = 2.7, 1.7 Hz, 1H), 1.36 (s, 9H)。 Compound PLC-4.4 : (2-(4-(tertiary butyl)phenyl)-4-phenyl-1H-pyrrole): Use KOH (17.66 mmol, 991 mg) in anhydrous THF (75 mL) and anhydrous PLC-4.2 (6.822 mmol, 2.220 g) was treated with MeOH (40 mL) and this solution was added dropwise to an ice-cold mixture of anhydrous methanol (40 mL) and 96% H 2 SO 4 (8.5 mL). After addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured into crushed ice and extracted with EtOAc (150 ml × 3). The combined organic phases were washed with 10% (w/w) Na2CO3 in H2O and then brine. After drying over anhydrous Na2SO4 , the solution was concentrated on a vacuum rotary evaporator to give the desired product PLC-4.3 as an oil, which was used in the next step without further purification. The crude product was confirmed to be dimethyl acetal by LCMS and NMR. The crude acetal was dissolved in acetic acid (15 mL) and treated with ammonium acetate (33.155 mmol). After heating at 100°C overnight, the reaction mixture was cooled to room temperature and water was added. The resulting precipitate was filtered off, dissolved in DCM and dried over MgSO4 . The crude precipitate was evaporated onto approximately 20 g of silica gel, and the silica gel was placed in a carrier. Purify by flash chromatography on silica gel (120 g, solids loading, equilibration 20% EtOAc/hexanes, elution 0% (2 CV) to 20% EtOAc/hexanes (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 1452 mg of the desired product PLC-4.4 was obtained as a light blue-violet solid (yield 77.3% from compound PLC 4.2). MS (APCI): Chemical formula: Calculated value for C 20 H 21 N (M+H) = 276; Experimental value: 276. 1H NMR (400 MHz, TCE) δ 8.51 (s, 1H), 7.63 - 7.55 (m, 2H), 7.50 - 7.41 (m, 4H), 7.38 (t, J = 7.7 Hz, 2H), 7.26 - 7.19 (m, 1H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.80 (dd , J = 2.7, 1.7 Hz, 1H), 1.36 (s, 9H).

化合物 PLC-4.5 (4-(3,7-雙(4-(三級丁基)苯基)-5,5-二氟-1,9-二苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲苯酚):以與 PLC-2.5(見下文)類似之方式,由 PLC-4.4(1.00 mmol,275 mg)及4-羥基-2,6-二甲基苯甲醛(0.500 mmol,75 mg)以及pTsOH.H 2O (0.200 mmol,38 mg),隨後在60℃下接著在50℃下在無水DCE (50 mL)中由DDQ (0.850 mmol,193 mg)及2× E t3N (4.00 mmol,0.56 mL)以及BF 3.OEt 2(6.00 mmol,0.74 mL)合成 PLC-4.5 將粗反應混合物用己烷稀釋,且負載至負載器中之約20 g矽膠上。藉由急驟層析在矽膠(120 g,固體負載,平衡0% EtOAc/己烷,溶離0% (2 CV)至20% EtOAc/己烷(20 CV))上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到219 mg深紅色固體(30%產率)。MS (APCI):化學式:C 49H 47BF 2N 2O (M+H)之計算值 = 729;實驗值:729。1H NMR (400 MHz, TCE) δ 7.96 - 7.89 (m, 4H), 7.56 - 7.46 (m, 4H), 7.05 - 6.98 (m, 2H), 6.98 - 6.90 (m, 4H), 6.86 - 6.76 (m, 4H), 6.51 (s, 2H), 5.70 (s, 2H), 4.21 (s, 1H), 1.98 (s, 6H), 1.38 (s, 18H)。 Compound PLC-4.5 : (4-(3,7-bis(4-(tertiary butyl)phenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrole And[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-xylenol): with PLC-2.5 (see (below) in a similar manner, composed of PLC-4.4 (1.00 mmol, 275 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (0.500 mmol, 75 mg) and pTsOH.H 2 O (0.200 mmol, 38 mg ) followed by DDQ (0.850 mmol, 193 mg) and 2× Et3N (4.00 mmol, 0.56 mL) and BF3.OEt2 (6.00) in anhydrous DCE (50 mL) at 60 °C and then at 50°C. mmol, 0.74 mL) to synthesize PLC-4.5 . The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica in a support vessel. Purify by flash chromatography on silica gel (120 g, solids loading, equilibration 0% EtOAc/hexanes, elution 0% (2 CV) to 20% EtOAc/hexanes (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 219 mg of dark red solid were obtained (30% yield). MS (APCI): Chemical formula: Calculated value of C 49 H 47 BF 2 N 2 O (M+H) = 729; Experimental value: 729. 1H NMR (400 MHz, TCE) δ 7.96 - 7.89 (m, 4H), 7.56 - 7.46 (m, 4H), 7.05 - 6.98 (m, 2H), 6.98 - 6.90 (m, 4H), 6.86 - 6.76 (m, 4H), 6.51 (s, 2H), 5.70 (s, 2H), 4.21 (s, 1H), 1.98 (s, 6H), 1.38 (s, 18H).

化合物 PLC-4 (2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(3,7-雙(4-(三級丁基)苯基)-5,5-二氟-1,9-二苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯):以與 PLC-2(見下文)類似之方式,由 PLC-4.5(0.075 mmol,55 mg)、 PLC-1.5(0.113 mmol,64 mg)、DMAP.pTsOH鹽(0.1108 mmol,33 mg)及EDC.HCl (0.0831 mmol,16 mg)合成 PLC-4。將粗反應混合物用己烷稀釋,且負載至負載器中之約20 g矽膠上。藉由急驟層析在矽膠(80 g固體負載,平衡0% EtOAc/己烷,溶離0% (2 CV)至50% EtOAc/己烷(30 CV))上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到81 mg深紅色固體(84%產率)。MS (APCI):化學式:C 82H 63BF 5N 3O 5(M+H)之計算值 = 1276;實驗值:1276。1H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.8 Hz, 1H), 8.65 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 8.3 Hz, 4H), 7.86 - 7.74 (m, 5H), 7.64 - 7.48 (m, 7H), 7.48 - 7.35 (m, 3H), 7.09 - 6.91 (m, 6H), 6.83 - 6.74 (m, 4H), 6.52 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.06 (s, 6H), 1.38 (s, 18H)。 Compound PLC-4 : (2-(4-(1,3-bisoxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def] Isoquinolin-2(3H)-yl)phenyl)acetic acid 4-(3,7-bis(4-(tertiary butyl)phenyl)-5,5-difluoro-1,9-diphenyl -5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethyl phenyl ester): In a similar manner to PLC-2 (see below), from PLC-4.5 (0.075 mmol, 55 mg), PLC-1.5 (0.113 mmol, 64 mg), DMAP.pTsOH salt (0.1108 mmol, 33 mg ) and EDC.HCl (0.0831 mmol, 16 mg) to synthesize PLC-4 . The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica in a support vessel. Purified by flash chromatography on silica gel (80 g solids loading, equilibration 0% EtOAc/hexanes, elution 0% (2 CV) to 50% EtOAc/hexanes (30 CV)). The product-containing fractions were evaporated to dryness in vacuo. 81 mg of dark red solid were obtained (84% yield). MS (APCI): Chemical formula: Calculated value of C 82 H 63 BF 5 N 3 O 5 (M+H) = 1276; Experimental value: 1276. 1H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.8 Hz , 1H), 8.65 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 8.3 Hz, 4H ), 7.86 - 7.74 (m, 5H), 7.64 - 7.48 (m, 7H), 7.48 - 7.35 (m, 3H), 7.09 - 6.91 (m, 6H), 6.83 - 6.74 (m, 4H), 6.52 (s , 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.06 (s, 6H), 1.38 (s, 18H).

化合物 PLC-2 之合成: Synthesis of compound PLC-2 :

化合物 PLC-2.1:((E)-1-(4-異丁基苯基)-3-苯基丙-2-烯-1-酮):以與 PLC-4.1相同之方式,在200標準酒精度之EtOH (10 mL)及水(4.70 mL)中由1-(4-異丁基苯基)乙-1-酮(19.57 mmol,3.540 g)、苯甲醛(19.57 mmol,2.077 g)及5N NaOH/水(23.48 mmol,4.70 mL)合成 PLC-2.1。得到4.844 g灰白色固體(94%產率)。MS (APCI):化學式:C 19H 20O (M+H)之計算值 = 265;實驗值:265。1H NMR (400 MHz, TCE) δ 7.99 - 7.92 (m, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.71 - 7.64 (m, 2H), 7.56 (d, J = 15.7 Hz, 1H), 7.45 (p, J = 3.5 Hz, 3H), 7.34 - 7.28 (m, 2H), 2.57 (d, J = 7.2 Hz, 2H), 1.92 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H)。 Compound PLC-2.1 : ((E)-1-(4-isobutylphenyl)-3-phenylprop-2-en-1-one): In the same way as PLC-4.1 , in 200 standard alcohol 1-(4-isobutylphenyl)ethan-1-one (19.57 mmol, 3.540 g), benzaldehyde (19.57 mmol, 2.077 g) and 5N in EtOH (10 mL) and water (4.70 mL) NaOH/water (23.48 mmol, 4.70 mL) was used to synthesize PLC-2.1 . 4.844 g of off-white solid were obtained (94% yield). MS (APCI): Chemical formula: Calculated value for C 19 H 20 O (M+H) = 265; found value: 265. 1H NMR (400 MHz, TCE) δ 7.99 - 7.92 (m, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.71 - 7.64 (m, 2H), 7.56 (d, J = 15.7 Hz, 1H), 7.45 (p, J = 3.5 Hz, 3H), 7.34 - 7.28 (m, 2H), 2.57 (d, J = 7.2 Hz, 2H), 1.92 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H).

化合物 PLC-2.2 (1-(4-異丁基苯基)-4-硝基-3-苯基丁-1-酮):以與 PLC-4.2相同之方式,在95℃下在硝基甲烷(15 mL)及200標準酒精度之乙醇(15 mL)中由 PLC-4.1(18.323 mmol,4.844 g)及KOH (2.346 mmol,137 mg)合成 PLC-2.2。以與 PLC-4.2相同之方式處理反應混合物,得到5.753 g棕色油狀物(其在室溫下極緩慢地固化) (97%產率)。MS (APCI):化學式:C 20H 23NO 3(M+H)之計算值 = 326;實驗值:326。1H NMR (400 MHz, TCE) δ 7.87 - 7.80 (m, 2H), 7.41 - 7.33 (m, 2H), 7.33 - 7.27 (m, 3H), 7.25 (d, J = 8.2 Hz, 2H), 4.85 (dd, J = 12.5, 6.3 Hz, 1H), 4.69 (dd, J = 12.5, 8.4 Hz, 1H), 4.20 (tt, J = 8.2, 6.2 Hz, 1H), 3.47 (dd, J = 17.9, 6.1 Hz, 1H), 3.39 (dd, J = 17.9, 7.8 Hz, 1H), 2.53 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.90 (d, J = 6.6 Hz, 6H)。 Compound PLC-2.2 : (1-(4-isobutylphenyl)-4-nitro-3-phenylbutan-1-one): in the same way as PLC-4.2 , in nitro at 95°C PLC-2.2 was synthesized from PLC-4.1 (18.323 mmol, 4.844 g) and KOH (2.346 mmol, 137 mg) in methane (15 mL) and 200 standard alcohol ethanol (15 mL). The reaction mixture was treated in the same manner as for PLC-4.2 , yielding 5.753 g of a brown oil that solidified very slowly at room temperature (97% yield). MS (APCI): Chemical formula: Calculated value for C 20 H 23 NO 3 (M+H) = 326; found value: 326. 1H NMR (400 MHz, TCE) δ 7.87 - 7.80 (m, 2H), 7.41 - 7.33 (m, 2H), 7.33 - 7.27 (m, 3H), 7.25 (d, J = 8.2 Hz, 2H), 4.85 (dd, J = 12.5, 6.3 Hz, 1H), 4.69 (dd, J = 12.5, 8.4 Hz, 1H), 4.20 (tt, J = 8.2, 6.2 Hz, 1H), 3.47 (dd, J = 17.9, 6.1 Hz, 1H), 3.39 (dd, J = 17.9, 7.8 Hz, 1H), 2.53 (d , J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.90 (d, J = 6.6 Hz, 6H).

化合物 PLC-2.3(2-(4-異丁基苯基)-4-苯基-1H-吡咯):以與 PLC-4.3相同之方式,在無水THF (200 mL)及無水甲醇(100 mL)中由 PLC-2.2(17.670 mmol,5.570 g)及KOH (45.765 mmol,2.568 g),隨後在0℃下由96% H 2SO 4(22 mL)及無水MeOH (100 mL)合成 PLC-2.3。以與 PLC-4.3相同之方式純化粗產物。得到2.981 g藍紫色固體(自PLC-2.2之產率61%)。MS (APCI):化學式:C 20H 21N (M+H)之計算值 = 276;實驗值:276。1H NMR (400 MHz, TCE) δ 8.51 (s, 1H), 7.61 - 7.55 (m, 2H), 7.48 - 7.42 (m, 2H), 7.38 (t, J = 7.7 Hz, 2H), 7.26 - 7.17 (m, 3H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.80 (dd, J = 2.8, 1.7 Hz, 1H), 2.50 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H)。 Compound PLC-2.3 (2-(4-isobutylphenyl)-4-phenyl-1H-pyrrole): in the same way as PLC-4.3 , in anhydrous THF (200 mL) and anhydrous methanol (100 mL) PLC-2.3 was synthesized from PLC-2.2 (17.670 mmol, 5.570 g) and KOH (45.765 mmol, 2.568 g), followed by 96% H 2 SO 4 (22 mL) and anhydrous MeOH (100 mL) at 0°C. The crude product was purified in the same manner as PLC-4.3 . 2.981 g of blue-violet solid was obtained (61% yield from PLC-2.2). MS (APCI): Chemical formula: Calculated value for C 20 H 21 N (M+H) = 276; Experimental value: 276. 1H NMR (400 MHz, TCE) δ 8.51 (s, 1H), 7.61 - 7.55 (m, 2H), 7.48 - 7.42 (m, 2H), 7.38 (t, J = 7.7 Hz, 2H), 7.26 - 7.17 (m, 3H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.80 (dd , J = 2.8, 1.7 Hz, 1H), 2.50 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H).

化合物 PLC-2.4 (4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-二苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲苯酚):以與 PLC-4.4相同之方式,由 PLC-2.3(2.00 mmol,551 mg)、4-羥基-2,6-二甲基苯甲醛(1.00 mmol,150 mg)及pTsOH.H 2O (0.300 mmol,57 mg),隨後在60℃下接著在50℃下在無水DCE (50 mL)中由DDQ (1.70 mmol,386 mg)及2× Et 3N (8.000 mmol,1.12 mL)及BF 3.OEt 2(12.00 mmol,1.48 mL)合成 PLC-2.4。以與 PLC-4.4相同之方式純化化合物,得到219 mg深紅色固體(30%產率)。MS (APCI):化學式:C 49H 47BF 2N 2O (M+H)之計算值 = 729;實驗值:729。1H NMR (400 MHz, TCE) δ 7.87 (d, J = 8.1 Hz, 4H), 7.26 (d, J = 8.2 Hz, 4H), 7.05 - 6.98 (m, 2H), 6.98 - 6.89 (m, 4H), 6.83 - 6.75 (m, 4H), 6.50 (s, 2H), 5.70 (s, 2H), 4.19 (s, 1H), 2.55 (d, J = 7.1 Hz, 4H), 2.03 - 1.84 (m, 8H), 0.94 (d, J = 6.6 Hz, 12H)。 Compound PLC-2.4 : (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1 ,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-xylenol): in the same way as PLC-4.4 , by PLC-2.3 (2.00 mmol, 551 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.00 mmol, 150 mg) and pTsOH.H 2 O (0.300 mmol, 57 mg), followed by 60°C PLC was then synthesized from DDQ (1.70 mmol, 386 mg) and 2× Et 3 N (8.000 mmol, 1.12 mL) and BF 3 .OEt 2 (12.00 mmol, 1.48 mL) in anhydrous DCE (50 mL) at 50 °C. -2.4 . The compound was purified in the same manner as PLC-4.4 to give 219 mg of a dark red solid (30% yield). MS (APCI): Chemical formula: Calculated value of C 49 H 47 BF 2 N 2 O (M+H) = 729; Experimental value: 729. 1H NMR (400 MHz, TCE) δ 7.87 (d, J = 8.1 Hz, 4H), 7.26 (d, J = 8.2 Hz, 4H), 7.05 - 6.98 (m, 2H), 6.98 - 6.89 (m, 4H), 6.83 - 6.75 (m, 4H), 6.50 (s, 2H), 5.70 (s, 2H), 4.19 (s, 1H), 2.55 (d, J = 7.1 Hz, 4H), 2.03 - 1.84 (m, 8H), 0.94 (d, J = 6.6 Hz, 12H).

化合物 PLC-2 (2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-二苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯):以與 PLC-4相同之方式,由 PLC-2.5(0.075 mmol,55 mg)、PLC-1.6 (0.113 mmol,64 mg)、DMAP.pTsOH鹽(0.1108 mmol,33 mg)及EDC.HCl (0.0831 mmol,16 mg)合成 PLC-2。以與PLC-4相同之方式純化產物,得到74 mg深紅色固體(77%產率)。MS (APCI):化學式:C 82H 63BF 5N 3O 5(M+H)之計算值 = 1276;實驗值:1276。1H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.9 Hz, 1H), 8.65 (d, J = 8.4 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 7.9 Hz, 4H), 7.84 - 7.77 (m, 5H), 7.62 - 7.57 (m, 2H), 7.55 (d, J = 8.6 Hz, 1H), 7.42 (d, J = 8.3 Hz, 1H), 7.41 - 7.36 (m, 2H), 7.27 (d, J = 8.0 Hz, 4H), 7.08 - 6.93 (m, 6H), 6.82 - 6.73 (m, 4H), 6.51 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.55 (d, J = 7.1 Hz, 4H), 2.05 (s, 6H), 1.92 (hept, J = 6.9 Hz, 2H), 0.95 (d, J = 6.6 Hz, 12H)。 Compound PLC-2 : (2-(4-(1,3-bisoxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def] Isoquinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethylphenyl ester) : In the same way as PLC-4 , from PLC-2.5 (0.075 mmol, 55 mg), PLC-1.6 (0.113 mmol, 64 mg), DMAP.pTsOH salt (0.1108 mmol, 33 mg) and EDC.HCl (0.0831 mmol, 16 mg) to synthesize PLC-2 . The product was purified in the same manner as PLC-4 to give 74 mg of a dark red solid (77% yield). MS (APCI): Chemical formula: Calculated value for C 82 H 63 BF 5 N 3 O 5 (M+H) = 1276; Experimental value: 1276. 1H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.9 Hz , 1H), 8.65 (d, J = 8.4 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 7.9 Hz, 4H ), 7.84 - 7.77 (m, 5H), 7.62 - 7.57 (m, 2H), 7.55 (d, J = 8.6 Hz, 1H), 7.42 (d, J = 8.3 Hz, 1H), 7.41 - 7.36 (m, 2H), 7.27 (d, J = 8.0 Hz, 4H), 7.08 - 6.93 (m, 6H), 6.82 - 6.73 (m, 4H), 6.51 (s, 2H), 6.10 (s, 2H), 3.90 (s , 2H), 2.55 (d, J = 7.1 Hz, 4H), 2.05 (s, 6H), 1.92 (hept, J = 6.9 Hz, 2H), 0.95 (d, J = 6.6 Hz, 12H).

化合物 PLC-5 之合成 Synthesis of compound PLC-5

化合物 PLC-5.1:(E)-3-苯基-1-(對甲苯基)丙-2-烯-1-酮:200 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物(4-甲基苯基)甲基酮(10.0 g,74.5 mmol)及苯甲醛(8.3 g,78.2 mmol)以及EtOH (100 ml)。向溶液中逐滴添加NaOH (17.9 mL,5 M於H 2O中)。在添加之後,將反應混合物在室溫下保持3小時。TLC及LCMS顯示反應完成。用50 mL H 2O稀釋反應混合物。藉由真空過濾收集產物且藉由50 mL H 2O/10 mL EtOH洗滌,隨後藉由凍乾進一步乾燥,得到呈白色固體狀之 PLC-5.1,其不經進一步純化即用於下一步驟。15.5 g,93%產率。MS (APCI):化學式:C 16H 14O ([M-H]-)之計算值 = 222,實驗值:222。1H NMR (400 MHz, CDCl3) 7.94 (m, 2H), 7.81 (d, J = 16.0 Hz, 1H), 7.65 (m, 2H), 7.54 (d, J = 16.0 Hz, 1H), 7.42 (m, 3H), 7.31 (m, 2H), 2.44 (s, 3H)。 Compound PLC-5.1 : (E)-3-phenyl-1-(p-tolyl)prop-2-en-1-one: A 200 mL flask was equipped with a stir bar. The compounds (4-methylphenyl)methyl ketone (10.0 g, 74.5 mmol) and benzaldehyde (8.3 g, 78.2 mmol) and EtOH (100 ml) were added to the flask. To the solution was added NaOH (17.9 mL, 5 M in H2O ) dropwise. After addition, the reaction mixture was kept at room temperature for 3 hours. TLC and LCMS showed the reaction was complete. Dilute the reaction mixture with 50 mL H2O . The product was collected by vacuum filtration and washed with 50 mL H2O /10 mL EtOH, followed by further drying by lyophilization to give PLC-5.1 as a white solid, which was used in the next step without further purification. 15.5 g, 93% yield. MS (APCI): Chemical formula: Calculated value of C 16 H 14 O ([MH]-) = 222, found value: 222. 1H NMR (400 MHz, CDCl3) 7.94 (m, 2H), 7.81 (d, J = 16.0 Hz, 1H), 7.65 (m, 2H), 7.54 (d, J = 16.0 Hz, 1H), 7.42 (m, 3H), 7.31 (m, 2H), 2.44 (s, 3H).

化合物 PLC-5.2:4-硝基-3-苯基-1-(對甲苯基)丁-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物 PLC-5.1(4.0 g,18.0 mmol)、硝基甲烷(20 mL)及EtOH (20 mL)。向混合物中添加KOH (201.9 mg,3.6 mmol)。在室溫下使反應混合物脫氣,且隨後加熱至95℃,且在此溫度下保持40分鐘。LCMS用於監測反應。在完成之後,將反應物冷卻至室溫,且藉由添加H 2O (200 ml)來處理。用EtOAc (150 mL ×3)萃取溶液。在萃取期間添加少量NaCl以輔助分離有機相與水相。合併之有機相經無水Na 2SO 4乾燥且藉由旋轉蒸發儀濃縮,得到呈棕色液體狀之 PLC-5.2,其不經進一步純化即用於下一步驟。全收量產率。MS (APCI):化學式:C 17H 17NO 3([M-H]-)之計算值 = 283,實驗值:283。1H NMR (400 MHz, CDCl 2CDCl 2) 7.83 (m, 2H), 7.32 (m, 7H), 4.85 (dd, J = 12.4 Hz, 6.4 Hz, 1H), 4.68 (dd, J = 12.4 Hz, 8.4 Hz, 1H), 4.20 (m, 1H), 3.42 (qd, J = 17.6 Hz, 6.0 Hz, 2H), 2.42 (s, 3H)。 Compound PLC-5.2 : 4-nitro-3-phenyl-1-(p-tolyl)butan-1-one: The 100 mL flask was equipped with a stirring rod. Compound PLC-5.1 (4.0 g, 18.0 mmol), nitromethane (20 mL) and EtOH (20 mL) were added to the flask. KOH (201.9 mg, 3.6 mmol) was added to the mixture. The reaction mixture was degassed at room temperature and then heated to 95°C and held at this temperature for 40 minutes. LCMS was used to monitor the reaction. After completion, the reaction was cooled to room temperature and treated by adding H2O (200 ml). The solution was extracted with EtOAc (150 mL ×3). A small amount of NaCl is added during extraction to assist in separating the organic and aqueous phases. The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated by rotary evaporator to give PLC-5.2 as a brown liquid, which was used in the next step without further purification. Full production yield. MS (APCI): Chemical formula: Calculated value for C 17 H 17 NO 3 ([MH]-) = 283, found value: 283. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.83 (m, 2H), 7.32 ( m, 7H), 4.85 (dd, J = 12.4 Hz, 6.4 Hz, 1H), 4.68 (dd, J = 12.4 Hz, 8.4 Hz, 1H), 4.20 (m, 1H), 3.42 (qd, J = 17.6 Hz , 6.0 Hz, 2H), 2.42 (s, 3H).

化合物 PLC-5.3 4,4-二甲氧基-3-苯基-1-(對甲苯基)丁-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物 PLC-5.2(5.1 g,18.0 mmol)、THF (200 mL)及MeOH (102 ml)。向溶液中一次性添加KOH (2.5 g,45.0 mmol)。將溶液在室溫下保持1小時。同時,將H 2SO 4(22 mL)於MeOH (106 mL)中之溶液冷卻至0℃。隨後,在0℃下經由另一漏斗將前述溶液逐滴添加至H 2SO 4溶液中。在添加之後,使反應物升溫至室溫。將反應物在室溫下再保持1小時。LCMS顯示反應完成。將反應溶液傾入碎冰中且用EtOAc (150 ml ×3)萃取。合併之有機相用含10% (w/w) Na 2CO 3之H 2O且隨後用鹽水洗滌。經無水Na 2SO 4乾燥之後,在真空旋轉蒸發儀下濃縮溶液,得到呈棕色油狀物之 PLC-5.3,其不經進一步純化即用於下一步驟。MS (APCI):化學式:C 19H 22O 3([M-H]-)之計算值 = 252,實驗值:252。1H NMR (400 MHz, CDCl 2CDCl 2) 7.82 (m, 2H), 7.28 (m, 7H), 4.46 (d, J = 5.6 Hz, 1H), 3.70 (m, 1H), 3.50 (dd, J = 17.6 Hz, 5.6 Hz, 1H), 3.35 (s, 3H), 3.34 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.29 (s, 3H), 2.41 (s, 3H)。 Compound PLC-5.3 : 4,4-Dimethoxy-3-phenyl-1-(p-tolyl)butan-1-one: The 100 mL flask was equipped with a stir bar. Compound PLC-5.2 (5.1 g, 18.0 mmol), THF (200 mL) and MeOH (102 ml) were added to the flask. KOH (2.5 g, 45.0 mmol) was added to the solution in one portion. Keep the solution at room temperature for 1 hour. Meanwhile, a solution of H2SO4 (22 mL) in MeOH (106 mL) was cooled to 0° C . Subsequently, the aforementioned solution was added dropwise to the H2SO4 solution via another funnel at 0°C. After addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured into crushed ice and extracted with EtOAc (150 ml × 3). The combined organic phases were washed with 10% (w/w) Na2CO3 in H2O and then brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated on a vacuum rotary evaporator to obtain PLC-5.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Chemical formula: Calculated value for C 19 H 22 O 3 ([MH]-) = 252, found value: 252. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.82 (m, 2H), 7.28 ( m, 7H), 4.46 (d, J = 5.6 Hz, 1H), 3.70 (m, 1H), 3.50 (dd, J = 17.6 Hz, 5.6 Hz, 1H), 3.35 (s, 3H), 3.34 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.29 (s, 3H), 2.41 (s, 3H).

化合物 PLC-5.4:4-苯基-2-(對甲苯基)-1H-吡咯:向100 ml燒瓶中裝入含 PLC-5.3(5.4 g,18.0 mmol)及NH 4•OAc (6.7 g,87.5 mmol)之AcOH (21.5 mL)。在室溫下使溶液脫氣。隨後將其加熱至100℃且在此溫度下保持攪拌5小時。TLC (50% EtOAc/己烷)顯示反應完成。反應混合物藉由添加H 2O (150 mL)淬滅且用DCM (150 mL×3)萃取。合併之有機相用飽和NaHCO 3及鹽水洗滌。經無水Na 2SO 4乾燥之後,在旋轉蒸發儀下濃縮溶液,且藉由矽膠急驟層析使用DCM/己烷(0%-100%)作為溶離劑來純化,得到3.5 g呈淡紫色固體狀之純化合物 PLC-5.4,三個步驟之產率82%。MS (APCI):化學式:C 17H 15N ([M-H]-)之計算值 = 233,實驗值:233。1H NMR (400 MHz, CDCl 2CDCl 2) δ 8.50 (s, 1H), 7.58 (m, 2H), 7.43 (m, 2H), 7.38 (m, 2H), 7.23 (m, 3H), 7.16 (m, 1H), 6.79 (m, 1H), 2,38 (s, 3H)。 Compound PLC-5.4 : 4-phenyl-2-(p-tolyl)-1H-pyrrole: A 100 ml flask was charged with PLC-5.3 (5.4 g, 18.0 mmol) and NH 4 •OAc (6.7 g, 87.5 mmol) in AcOH (21.5 mL). Degas the solution at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 hours. TLC (50% EtOAc/Hexane) showed the reaction was complete. The reaction mixture was quenched by adding H2O (150 mL) and extracted with DCM (150 mL×3). The combined organic phases were washed with saturated NaHCO 3 and brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated under a rotary evaporator, and purified by silica gel flash chromatography using DCM/hexane (0%-100%) as the eluent to obtain 3.5 g of a lavender solid. The pure compound PLC-5.4 , the yield of three steps was 82%. MS (APCI): Chemical formula: Calculated value of C 17 H 15 N ([MH]-) = 233, found value: 233. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) δ 8.50 (s, 1H), 7.58 ( m, 2H), 7.43 (m, 2H), 7.38 (m, 2H), 7.23 (m, 3H), 7.16 (m, 1H), 6.79 (m, 1H), 2,38 (s, 3H).

化合物 PLC-5.5:4-(5,5-二氟-1,9-二苯基-3,7-二對甲苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲苯酚:100 mL 2頸圓底燒瓶裝配有空氣冷凝器及攪拌棒。向燒瓶中添加 PLC-5.4(530.0 mg,2.3 mmol)及4-羥基-2,6-二甲基苯甲醛(170.6 mg,1.1 mmol),接著添加無水二氯乙烷(DCE,25 ml)。反應混合物用Ar鼓泡30分鐘,隨後添加p-TsOH•H 2O (38.0 mg,0.2 mmol)。將反應溶液加熱至60℃且在此溫度下保持過夜。隨後將反應物冷卻至室溫且添加DDQ (412.0 mg,1.8 mmol)。將反應物在室溫下保持30分鐘。隨後在室溫下添加BF 3•OEt 2(0.84 mL,6.8 mmol)及Et 3N (0.63 mL,4.6 mmol)。將反應混合物加熱至50℃且在此溫度下保持1小時。在室溫下添加更多BF 3•OEt 2(1.2 mL)及Et 3N (0.8 mL)。將反應混合物在50℃下再保持1小時。反應混合物用矽膠負載,且藉由急驟層析使用DCM/己烷(0-100%)作為溶離劑來純化,得到333.0 mg呈深紫色至金色固體狀之純 PLC-5.5,45%產率。MS (APCI):化學式:C 43H 35BF 2N 2O ([M-H]-)之計算值 = 644,實驗值:644。1H NMR (400 MHz, CDCl 2CDCl 2) 7.83 (m, 4H), 7.30 (m, 4H), 7.01 (m, 2H), 6.93 (m, 4H), 6.79 (m, 4H), 6.45 (s, 2H), 5.70 (s, 2H), 4.21 (s, 1H), 2.44 (s, 6H), 1.98 (s, 6H)。 Compound PLC-5.5 : 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-xylenol: 100 mL 2-neck round-bottom flask equipped with air condenser and stirring rod. PLC-5.4 (530.0 mg, 2.3 mmol) and 4-hydroxy-2,6-dimethylbenzaldehyde (170.6 mg, 1.1 mmol) were added to the flask, followed by anhydrous dichloroethane (DCE, 25 ml). The reaction mixture was bubbled with Ar for 30 min, then p-TsOH·H 2 O (38.0 mg, 0.2 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction was then cooled to room temperature and DDQ (412.0 mg, 1.8 mmol) was added. The reaction was kept at room temperature for 30 minutes. BF 3 •OEt 2 (0.84 mL, 6.8 mmol) and Et 3 N (0.63 mL, 4.6 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and maintained at this temperature for 1 hour. Add more BF 3 •OEt 2 (1.2 mL) and Et 3 N (0.8 mL) at room temperature. The reaction mixture was held at 50°C for an additional hour. The reaction mixture was supported on silica gel and purified by flash chromatography using DCM/hexane (0-100%) as the eluent to obtain 333.0 mg of pure PLC-5.5 as a dark purple to golden solid, 45% yield. MS (APCI): Chemical formula: Calculated value of C 43 H 35 BF 2 N 2 O ([MH]-) = 644, found value: 644. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.83 (m, 4H) , 7.30 (m, 4H), 7.01 (m, 2H), 6.93 (m, 4H), 6.79 (m, 4H), 6.45 (s, 2H), 5.70 (s, 2H), 4.21 (s, 1H), 2.44 (s, 6H), 1.98 (s, 6H).

化合物 PLC-5:2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-1,9-二苯基-3,7-二對甲苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加化合物1644-31 (65.0 mg,0.10 mmol)、1621-29 (84.5 mg,0.15 mmol)、DIC (50.5 mg,0.40 mmol)及DMAP•TsOH (58.8 mg,0.20 mmol),接著添加無水DCM (7 ml)。將反應混合物在室溫下保持過夜。反應完成之後,反應混合物用矽膠負載,且藉由急驟層析使用DCM/己烷(20%-100%)及EtOAc/DCM (0-8%)作為溶離劑來純化,得到呈深紫紅色固體狀之純1644-32。固體用MeOH (10 ml)進一步濕磨,得到61.0 mg PLC-5,51%產率。MS (APCI):化學式:C 76H 51BF 5N 3O 5([M-H]-)之計算值 = 1192,實驗值:1192。1H NMR (400 MHz, CDCl 2CDCl 2) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.82 (m, 9H), 7.58 (m, 3H), 7.40 (m, 3H), 7.30 (m, 4H), 6.99 (m, 6H), 6.78 (m, 4H), 6.46 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.44 (s, 6H), 2.06 (s, 6H)。 Compound PLC-5 : 2-(4-(1,3-dilateral oxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def]iso Quinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrolo [1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethylphenyl ester: 25 mL vial equipped with stir bar . Compounds 1644-31 (65.0 mg, 0.10 mmol), 1621-29 (84.5 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol), and DMAP·TsOH (58.8 mg, 0.20 mmol) were added to the vial, followed by anhydrous DCM (7 ml). The reaction mixture was kept at room temperature overnight. After the reaction was completed, the reaction mixture was loaded with silica gel and purified by flash chromatography using DCM/hexane (20%-100%) and EtOAc/DCM (0-8%) as eluents to obtain a deep purple solid. The pure state of affairs 1644-32. The solid was further triturated with MeOH (10 ml) to give 61.0 mg of PLC-5 in 51% yield. MS (APCI): Chemical formula: Calculated value of C 76 H 51 BF 5 N 3 O 5 ([MH]-) = 1192, experimental value: 1192. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.82 (m, 9H), 7.58 (m, 3H), 7.40 (m, 3H), 7.30 (m, 4H), 6.99 (m, 6H), 6.78 (m, 4H), 6.46 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.44 (s, 6H), 2.06 (s, 6H).

化合物 PLC-6 之合成 Synthesis of compound PLC-6

化合物 PLC-6:2-(4-(9-(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-1,9-二苯基-3,7-二對甲苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加化合物PLC-5.5 (65.0 mg,0.10 mmol)、化合物 6.1(95.0 mg,0.15 mmol,參見2022年9月23日申請之PCT/US2022/076912中之合成程序)、DIC (50.5 mg,0.40 mmol)及DMAP•TsOH (58.8 mg,0.20 mmol),接著添加無水DCM (7 ml)。將反應混合物在室溫下保持過夜。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/DCM (0-8%-14%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-6。固體用MeOH (10 ml)進一步濕磨,得到48.0 mg 1644-34,38%產率。MS (APCI):化學式:C 77H 50BF 8N 3O 5([M-H]-)之計算值 = 1260,實驗值:1260。1H NMR (400 MHz, CDCl2CDCl2) 8.71 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.4 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.11 (bs, 2H), 7.96 (bs, 1H), 7.83 (m, 4H), 7.82 (dd, J = 8.0 Hz, 2.4 Hz, 1H), 7.59 (m, 3H), 7.42 (m, 3H), 7.30 (m, 4H), 6.99 (m, 6H), 6.78 (m, 4H), 6.46 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.44 (s, 6H), 2.06 (s, 6H)。 Compound PLC-6 : 2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dilateral oxy-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4- Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethylphenyl ester: 25 mL vial assembly There is a stir stick. Add compound PLC-5.5 (65.0 mg, 0.10 mmol), compound 6.1 (95.0 mg, 0.15 mmol, see the synthesis procedure in PCT/US2022/076912 filed on September 23, 2022), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol), followed by anhydrous DCM (7 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/DCM (0-8%-14%) as the eluent to obtain pure PLC-6 as a deep purple solid. The solid was further triturated with MeOH (10 ml) to afford 48.0 mg of 1644-34, 38% yield. MS (APCI): Chemical formula: Calculated value of C 77 H 50 BF 8 N 3 O 5 ([MH]-) = 1260, found value: 1260. 1H NMR (400 MHz, CDCl2CDCl2) 8.71 (d, J = 8.0 Hz , 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.4 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.11 (bs, 2H), 7.96 (bs , 1H), 7.83 (m, 4H), 7.82 (dd, J = 8.0 Hz, 2.4 Hz, 1H), 7.59 (m, 3H), 7.42 (m, 3H), 7.30 (m, 4H), 6.99 (m , 6H), 6.78 (m, 4H), 6.46 (s, 2H), 6.10 (s, 2H), 3.90 (s, 2H), 2.44 (s, 6H), 2.06 (s, 6H).

化合物 PLC-7 之合成 Synthesis of compound PLC-7

化合物 PLC-7:4-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)丁酸4-(5,5-二氟-1,9-二苯基-3,7-二對甲苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加化合物 PLC-5.5(65.0 mg,0.10 mmol)、PLC-3.5 (89.0 mg,0.15 mmol)、DIC (50.5 mg,0.40 mmol)及DMAP•TsOH (58.8 mg,0.20 mmol),接著添加無水DCM (7 ml)。將反應混合物在室溫下保持過夜。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/己烷(0-60%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-7。固體用MeOH (10 ml)進一步濕磨,得到115.0 mg PLC-7,94%產率。MS (APCI):化學式:C 78H 55BF 5N 3O 5([M-H]-)之計算值 = 1220,實驗值:1220。1H NMR (400 MHz, CDCl2CDCl2) 8.60 (d, J = 8.0 Hz, 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.20 (d, J = 2.4 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.73 (m, 9H), 7.46 (d, J = 2.8 Hz, 1H), 7.38 (m, 2H), 7.34 (d, J = 2.8 Hz, 1H), 7.22 (m, 5H), 7.19 (dd, J = 8.0 Hz, 2.4 Hz, 1H), 6.91 (m, 6H), 6.69 (m, 4H), 6.37 (s, 2H), 5.99 (s, 2H), 2.77 (t, J = 7.6 Hz, 2H), 2.47 (d, J = 7.6 Hz, 2H), 2.35 (s, 6H), 2.05 (m, 2H), 1.96 (s, 6H)。 Compound PLC-7 : 4-(4-(1,3-dilateral oxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def]iso Quinolin-2(3H)-yl)phenyl)butyrate 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrole And[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-dimethylphenyl ester: 25 mL vial equipped with stirrer Great. Add compounds PLC-5.5 (65.0 mg, 0.10 mmol), PLC-3.5 (89.0 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol) to the vial, followed by anhydrous DCM (7 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/hexane (0-60%) as the eluent to obtain pure PLC-7 as a deep purple solid. The solid was further triturated with MeOH (10 ml) to give 115.0 mg of PLC-7, 94% yield. MS (APCI): Chemical formula: Calculated value of C 78 H 55 BF 5 N 3 O 5 ([MH]-) = 1220, found value: 1220. 1H NMR (400 MHz, CDCl2CDCl2) 8.60 (d, J = 8.0 Hz , 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.20 (d, J = 2.4 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.73 (m, 9H), 7.46 (d , J = 2.8 Hz, 1H), 7.38 (m, 2H), 7.34 (d, J = 2.8 Hz, 1H), 7.22 (m, 5H), 7.19 (dd, J = 8.0 Hz, 2.4 Hz, 1H), 6.91 (m, 6H), 6.69 (m, 4H), 6.37 (s, 2H), 5.99 (s, 2H), 2.77 (t, J = 7.6 Hz, 2H), 2.47 (d, J = 7.6 Hz, 2H ), 2.35 (s, 6H), 2.05 (m, 2H), 1.96 (s, 6H).

化合物 PLC-8 之合成 Synthesis of compound PLC-8

化合物 PLC-8.1:(E)-1-(對甲苯基)-3-(4-(三氟甲基)苯基)丙-2-烯-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物(4-甲基苯基)甲基酮(2.0 g,14.9 mmol)及4-三氟甲基苯甲醛(2.7 g,15.6 mmol)以及EtOH (15 ml)。向溶液中逐滴添加NaOH (3.6 mL,5 M於H 2O中)。在添加之後,將反應混合物在室溫下保持1小時。TLC及LCMS顯示反應完成。用50 mL H 2O稀釋反應混合物。藉由真空過濾收集產物且藉由50 mL H 2O洗滌,隨後藉由凍乾進一步乾燥,得到呈白色固體狀之 PLC-8.1,其不經進一步純化即用於下一步驟。4.25 g,98%產率。MS (APCI):化學式:C 17H 13F 3O ([M-H]-)之計算值 = 290,實驗值:290。1H NMR (400 MHz, CDCl3) 7.94 (m, 2H), 7.83 (d, J = 16.0 Hz, 1H), 7.76 (m, 2H), 7.69 (m, 2H), 7.60 (d, J = 16.0 Hz, 1H), 7.35 (m, 2H), 2.44 (s, 3H)。 Compound PLC-8.1 : (E)-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one: A 100 mL flask was equipped with a stir bar. The compounds (4-methylphenyl)methylketone (2.0 g, 14.9 mmol) and 4-trifluoromethylbenzaldehyde (2.7 g, 15.6 mmol) and EtOH (15 ml) were added to the flask. To the solution was added NaOH (3.6 mL, 5 M in H2O ) dropwise. After addition, the reaction mixture was kept at room temperature for 1 hour. TLC and LCMS showed the reaction was complete. Dilute the reaction mixture with 50 mL H2O . The product was collected by vacuum filtration and washed with 50 mL H2O , followed by further drying by lyophilization to give PLC-8.1 as a white solid, which was used in the next step without further purification. 4.25 g, 98% yield. MS (APCI): Chemical formula: Calculated value for C 17 H 13 F 3 O ([MH]-) = 290, found value: 290. 1H NMR (400 MHz, CDCl3) 7.94 (m, 2H), 7.83 (d, J = 16.0 Hz, 1H), 7.76 (m, 2H), 7.69 (m, 2H), 7.60 (d, J = 16.0 Hz, 1H), 7.35 (m, 2H), 2.44 (s, 3H).

化合物 PLC-8.2:4-硝基-1-(對甲苯基)-3-(4-(三氟甲基)苯基)丁-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加 PLC-8.1(2.0 g,6.9 mmol)、硝基甲烷(8 mL)及EtOH (8 mL)。向混合物中添加KOH (77.4 mg,1.4 mmol)。在室溫下使反應混合物脫氣,且隨後加熱至95℃,且在此溫度下保持30分鐘。LCMS用於監測反應。在完成之後,將反應物冷卻至室溫,且藉由添加H 2O (150 ml)來處理。用EtOAc (100 mL ×3)萃取溶液。在萃取期間添加少量NaCl以輔助分離有機相與水相。合併之有機相經無水Na 2SO 4乾燥且藉由旋轉蒸發儀濃縮,得到呈棕色液體狀之 PLC-8.2,其不經進一步純化即用於下一步驟。全收量產率。MS (APCI):化學式:C 18H 16F 3NO 3([M+H]+)之計算值 = 352,實驗值:352。1H NMR (400 MHz, CDCl2CDCl2) 7.81 (m, 2H), 7.61 (m, 2H), 7.43 (m, 2H), 7.28 (m, 2H), 4.88 (dd, J = 12.8 Hz, 6.0 Hz, 1H), 4.71 (dd, J = 12.8 Hz, 8.4 Hz, 1H), 4.28 (m, 1H), 3.42 (qd, J = 17.6 Hz, 6.4 Hz, 2H), 2.42 (s, 3H)。 Compound PLC-8.2 : 4-nitro-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 100 mL flask was equipped with a stirring rod. Add PLC-8.1 (2.0 g, 6.9 mmol), nitromethane (8 mL), and EtOH (8 mL) to the flask. KOH (77.4 mg, 1.4 mmol) was added to the mixture. The reaction mixture was degassed at room temperature and then heated to 95°C and held at this temperature for 30 minutes. LCMS was used to monitor the reaction. After completion, the reaction was cooled to room temperature and treated by adding H2O (150 ml). The solution was extracted with EtOAc (100 mL ×3). A small amount of NaCl is added during extraction to assist in separating the organic and aqueous phases. The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated by rotary evaporator to obtain PLC-8.2 as a brown liquid, which was used in the next step without further purification. Full production yield. MS (APCI): Chemical formula: Calculated value for C 18 H 16 F 3 NO 3 ([M+H]+) = 352, found value: 352. 1H NMR (400 MHz, CDCl2CDCl2) 7.81 (m, 2H), 7.61 (m, 2H), 7.43 (m, 2H), 7.28 (m, 2H), 4.88 (dd, J = 12.8 Hz, 6.0 Hz, 1H), 4.71 (dd, J = 12.8 Hz, 8.4 Hz, 1H), 4.28 (m, 1H), 3.42 (qd, J = 17.6 Hz, 6.4 Hz, 2H), 2.42 (s, 3H).

化合物 PLC-8.3:4,4-二甲氧基-1-(對甲苯基)-3-(4-(三氟甲基)苯基)丁-1-酮:250 mL燒瓶裝配有攪拌棒。向燒瓶中添加 PLC-8.2(2.4 g,6.9 mmol)、THF (77 mL)及MeOH (39 ml)。向溶液中一次性添加KOH (967.9 mg,17.3 mmol)。將溶液在室溫下保持1小時。同時,將H 2SO 4(9 mL)於MeOH (41 mL)中之溶液冷卻至0℃。隨後,在0℃下經由另一漏斗將前述溶液逐滴添加至H 2SO 4溶液中。在添加之後,使反應物升溫至室溫。將反應物在室溫下再保持1小時。LCMS顯示反應完成。將反應溶液傾入碎冰中且用EtOAc (150 ml ×3)萃取。合併之有機相用含10% (w/w) Na 2CO 3之H 2O且隨後用鹽水洗滌。經無水Na 2SO 4乾燥之後,在真空旋轉蒸發儀下濃縮溶液,得到呈棕色油狀物之 PLC-8.3,其不經進一步純化即用於下一步驟。MS (APCI):化學式:C 20H 21F 3O 3([M-OMe]+)之計算值 = 335,實驗值:335。1H NMR (400 MHz, CDCl 2CDCl 2) 7.82 (m, 2H), 7.55 (m, 2H), 7.46 (m, 2H), 7.26 (m, 2H), 4.46 (d, J = 5.2 Hz, 1H), 3.78 (td, J = 9.2 Hz, 5.2 Hz, 1H), 3.53 (dd, J = 17.6 Hz, 4.8 Hz, 1H), 3.37 (s, 3H), 3.36 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.31 (s, 3H), 2.41 (s, 3H)。 Compound PLC-8.3 : 4,4-Dimethoxy-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 250 mL flask was equipped with a stirring rod. Add PLC-8.2 (2.4 g, 6.9 mmol), THF (77 mL) and MeOH (39 ml) to the flask. KOH (967.9 mg, 17.3 mmol) was added to the solution in one portion. Keep the solution at room temperature for 1 hour. Meanwhile, a solution of H2SO4 (9 mL) in MeOH (41 mL) was cooled to 0° C . Subsequently, the aforementioned solution was added dropwise to the H2SO4 solution via another funnel at 0°C. After addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured into crushed ice and extracted with EtOAc (150 ml × 3). The combined organic phases were washed with 10% (w/w) Na2CO3 in H2O and then brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated on a vacuum rotary evaporator to obtain PLC-8.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Chemical formula: Calculated value of C 20 H 21 F 3 O 3 ([M-OMe]+) = 335, experimental value: 335. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.82 (m, 2H ), 7.55 (m, 2H), 7.46 (m, 2H), 7.26 (m, 2H), 4.46 (d, J = 5.2 Hz, 1H), 3.78 (td, J = 9.2 Hz, 5.2 Hz, 1H), 3.53 (dd, J = 17.6 Hz, 4.8 Hz, 1H), 3.37 (s, 3H), 3.36 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.31 (s, 3H), 2.41 (s, 3H) .

化合物 PLC-8.4:2-(對甲苯基)-4-(4-(三氟甲基)苯基)-1H-吡咯:向100 ml燒瓶中裝入含 PLC-8.3(2.5 g,6.9 mmol)及NH 4•OAc (2.6 g,33.5 mmol)之AcOH (8.5 mL)。在室溫下使溶液脫氣。隨後將其加熱至100℃且在此溫度下保持攪拌5小時。TLC (50% EtOAc/己烷)顯示反應完成。反應混合物藉由添加H 2O (40 mL)淬滅且用DCM (60 mL×3)萃取。合併之有機相用飽和NaHCO 3及鹽水洗滌。經無水Na 2SO 4乾燥之後,在旋轉蒸發儀下濃縮溶液,且藉由矽膠急驟層析使用DCM/己烷(0%-100%)作為溶離劑來純化,得到1.4 g呈藍色固體狀之純 PLC-8.4,三個步驟之產率65%。MS (APCI):化學式:C 18H 14F 3N ([M-H]-)之計算值 = 300,實驗值:300。1H NMR (400 MHz, CDCl 2CDCl 2) δ 8.59 (s, 1H), 7.67 (m, 2H), 7.61 (m, 2H), 7.44 (m, 2H), 7.24 (m, 3H), 6.80 (m, 1H), 2.39 (s, 3H)。 Compound PLC-8.4 : 2-(p-tolyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole: A 100 ml flask was charged with PLC-8.3 (2.5 g, 6.9 mmol) and NH 4 •OAc (2.6 g, 33.5 mmol) in AcOH (8.5 mL). Degas the solution at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 hours. TLC (50% EtOAc/Hexane) showed the reaction was complete. The reaction mixture was quenched by adding H2O (40 mL) and extracted with DCM (60 mL×3). The combined organic phases were washed with saturated NaHCO 3 and brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated under a rotary evaporator, and purified by silica gel flash chromatography using DCM/hexane (0%-100%) as the eluent to obtain 1.4 g of a blue solid. Pure PLC-8.4 , the yield of three steps is 65%. MS (APCI): Chemical formula: Calculated value of C 18 H 14 F 3 N ([MH]-) = 300, experimental value: 300. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) δ 8.59 (s, 1H), 7.67 (m, 2H), 7.61 (m, 2H), 7.44 (m, 2H), 7.24 (m, 3H), 6.80 (m, 1H), 2.39 (s, 3H).

化合物 PLC-8.5:4-(5,5-二氟-3,7-二對甲苯基-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲苯酚:100 mL 2頸圓底燒瓶裝配有空氣冷凝器及攪拌棒。向燒瓶中添加 PLC-8.4(602.6 mg,2.0 mmol)及4-羥基-2,6-二甲基苯甲醛(150.2 mg,1.0 mmol),接著添加無水二氯乙烷(22 mL)。反應混合物用Ar鼓泡30分鐘,隨後添加p-TsOH•H 2O (34.2 mg,0.2 mmol)。將反應溶液加熱至60℃且在此溫度下保持過夜。隨後將反應物冷卻至室溫且添加DDQ (454.0 mg,2.0 mmol)。將反應物在室溫下保持30分鐘。隨後在室溫下添加BF 3•OEt 2(1.5 mL,12.0 mmol)及Et 3N (1.1 mL,8.0 mmol)。將反應混合物加熱至50℃且在此溫度下保持2小時。反應混合物用矽膠負載,且藉由急驟層析使用DCM/己烷(0-100%)作為溶離劑來純化,得到642.0 mg呈深紫藍色固體狀之純 PLC-8.5,82%產率。MS (APCI):化學式:C 45H 33BF 8N 2O ([M-H]-)之計算值 = 780,實驗值:780。1H NMR (400 MHz, CDCl 2CDCl 2) 7.83 (m, 4H), 7.31 (m, 4H), 7.20 (4H), 6.90 (m, 4H), 6.50 (s, 2H), 5.70 (s, 2H), 4.36 (bs, 1H), 2.44 (s, 6H), 1.95 (s, 6H)。 Compound PLC-8.5 : 4-(5,5-difluoro-3,7-di-p-tolyl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrole And[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-xylenol: 100 mL 2-neck round bottom flask assembly There is an air condenser and stirring rod. PLC-8.4 (602.6 mg, 2.0 mmol) and 4-hydroxy-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol) were added to the flask, followed by anhydrous dichloroethane (22 mL). The reaction mixture was bubbled with Ar for 30 min, then p-TsOH·H 2 O (34.2 mg, 0.2 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction was then cooled to room temperature and DDQ (454.0 mg, 2.0 mmol) was added. The reaction was kept at room temperature for 30 minutes. BF 3 •OEt 2 (1.5 mL, 12.0 mmol) and Et 3 N (1.1 mL, 8.0 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and maintained at this temperature for 2 hours. The reaction mixture was supported on silica gel and purified by flash chromatography using DCM/hexane (0-100%) as the eluent to obtain 642.0 mg of pure PLC-8.5 as a deep purple-blue solid, 82% yield. MS (APCI): Chemical formula: Calculated value of C 45 H 33 BF 8 N 2 O ([MH]-) = 780, found value: 780. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.83 (m, 4H) , 7.31 (m, 4H), 7.20 (4H), 6.90 (m, 4H), 6.50 (s, 2H), 5.70 (s, 2H), 4.36 (bs, 1H), 2.44 (s, 6H), 1.95 ( s, 6H).

化合物 PLC-8:2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-3,7-二對甲苯基-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加 PLC-8.5(78.0 mg,0.10 mmol)、PLC-1.5 (84.5 mg,0.15 mmol)、DIC (50.5 mg,0.40 mmol)及DMAP•TsOH (58.8 mg,0.20 mmol),接著添加無水DCM (8 ml)。將反應混合物在室溫下保持過夜。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/DCM (0-8%-10%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-8。固體用MeOH (10 ml)進一步濕磨,得到15.0 mg PLC-8,11%產率。MS (APCI):化學式:C 78H 49BF 11N 3O 5([M-H]-)之計算值 = 1327,實驗值:1327。1H NMR (400 MHz, CDCl 2CDCl 2) 8.71 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.82 (m, 9H), 7.56 (m, 3H), 7.34 (m, 11H), 6.90 (m, 4H), 6.51 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.45 (s, 6H), 2.05 (s, 6H)。 Compound PLC-8 : 2-(4-(1,3-dilateral oxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def]iso Quinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-3,7-di-p-tolyl-1,9-bis(4-(trifluoromethyl)phenyl) -5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethyl Phenyl Ester: 25 mL vial equipped with stir bar. Add PLC-8.5 (78.0 mg, 0.10 mmol), PLC-1.5 (84.5 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol), and DMAP·TsOH (58.8 mg, 0.20 mmol) to the vial, followed by anhydrous DCM (8ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/DCM (0-8%-10%) as the eluent to obtain pure PLC-8 as a deep purple solid. The solid was further triturated with MeOH (10 ml) to give 15.0 mg of PLC-8, 11% yield. MS (APCI): Chemical formula: Calculated value of C 78 H 49 BF 11 N 3 O 5 ([MH]-) = 1327, experimental value: 1327. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 8.71 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.82 (m, 9H), 7.56 (m, 3H), 7.34 (m, 11H), 6.90 (m, 4H), 6.51 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.45 (s, 6H), 2.05 (s, 6H).

化合物 PLC-9 之合成 Synthesis of compound PLC-9

化合物 PLC-9.1 (E)-1-(4-異丁基苯基)-3-(4-(三氟甲基)苯基)丙-2-烯-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物(4-異丁基苯基)甲基酮(2.0 g,11.3 mmol)及4-三氟甲基苯甲醛(2.1 g,11.9 mmol)以及EtOH (15 ml)。向溶液中逐滴添加NaOH (2.7 mL,5 M於H 2O中)。在添加之後,將反應混合物在室溫下保持1小時。TLC及LCMS顯示反應完成。用50 mL H 2O稀釋反應混合物。藉由真空過濾收集產物且藉由50 mL H 2O洗滌,隨後藉由凍乾進一步乾燥,得到呈白色固體狀之PLC-9.1,其不經進一步純化即用於下一步驟。3.66 g,97%產率。MS (APCI):化學式:C 20H 19F 3O ([M-H]-)之計算值 = 332,實驗值:332。1H NMR (400 MHz, CDCl3) 7.96 (m, 2H), 7.79 (d, J = 16.0 Hz, 1H), 7.77 (m, 2H), 7.70 (m, 2H), 7.61 (d, J = 16.0 Hz, 1H), 7.32 (m, 2H), 2.58 (d, J = 7.2 Hz, 2H), 1.93 (m, 1H), 0.94 (d, J = 6.8 Hz, 6H)。 Compound PLC-9.1 : (E)-1-(4-isobutylphenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one: 100 mL flask equipped with Stirring stick. The compounds (4-isobutylphenyl)methyl ketone (2.0 g, 11.3 mmol) and 4-trifluoromethylbenzaldehyde (2.1 g, 11.9 mmol) and EtOH (15 ml) were added to the flask. To the solution was added NaOH (2.7 mL, 5 M in H2O ) dropwise. After addition, the reaction mixture was kept at room temperature for 1 hour. TLC and LCMS showed the reaction was complete. Dilute the reaction mixture with 50 mL H2O . The product was collected by vacuum filtration and washed with 50 mL H2O , followed by further drying by lyophilization to give PLC-9.1 as a white solid, which was used in the next step without further purification. 3.66 g, 97% yield. MS (APCI): Chemical formula: Calculated value for C 20 H 19 F 3 O ([MH]-) = 332, found value: 332. 1H NMR (400 MHz, CDCl3) 7.96 (m, 2H), 7.79 (d, J = 16.0 Hz, 1H), 7.77 (m, 2H), 7.70 (m, 2H), 7.61 (d, J = 16.0 Hz, 1H), 7.32 (m, 2H), 2.58 (d, J = 7.2 Hz, 2H), 1.93 (m, 1H), 0.94 (d, J = 6.8 Hz, 6H).

化合物 PLC-9.2 1-(4-異丁基苯基)-4-硝基-3-(4-(三氟甲基)苯基)丁-1-酮:100 mL燒瓶裝配有攪拌棒。向燒瓶中添加 PLC-9.1(2.0 g,6.0 mmol)、硝基甲烷(7 mL)及EtOH (7 mL)。向混合物中添加KOH (67.3 mg,1.2 mmol)。在室溫下使反應混合物脫氣,且隨後加熱至95℃,且在此溫度下保持30分鐘。LCMS用於監測反應。在完成之後,將反應物冷卻至室溫,且藉由添加H 2O (150 ml)來處理。用EtOAc (100 mL ×3)萃取溶液。在萃取期間添加少量NaCl以輔助分離有機相與水相。合併之有機相經無水Na 2SO 4乾燥且藉由旋轉蒸發儀濃縮,得到呈棕色液體狀之 PLC-9.2,其不經進一步純化即用於下一步驟。全收量產率。MS (APCI):化學式:C 21H 22F 3NO 3([M+H]+)之計算值 = 394,實驗值:394。1H NMR (400 MHz, CDCl 2CDCl 2) 7.83 (m, 2H), 7.62 (m, 2H), 7.44 (m, 2H), 7.25 (m, 2H), 4.88 (dd, J = 12.8 Hz, 6.0 Hz, 1H), 4.71 (dd, J = 12.8 Hz, 8.4 Hz, 1H), 4.29 (m, 1H), 3.43 (qd, J = 18.0 Hz, 7.6 Hz, 2H), 2.53 (d, J = 7.2 Hz, 2H), 1.87 (m, 1 H), 0.90 (d, J = 7.8 Hz, 6H), Compound PLC-9.2 : 1-(4-isobutylphenyl)-4-nitro-3-(4-(trifluoromethyl)phenyl)butan-1-one: The 100 mL flask was equipped with a stir bar. Add PLC-9.1 (2.0 g, 6.0 mmol), nitromethane (7 mL), and EtOH (7 mL) to the flask. KOH (67.3 mg, 1.2 mmol) was added to the mixture. The reaction mixture was degassed at room temperature and then heated to 95°C and held at this temperature for 30 minutes. LCMS was used to monitor the reaction. After completion, the reaction was cooled to room temperature and treated by adding H2O (150 ml). The solution was extracted with EtOAc (100 mL ×3). A small amount of NaCl is added during extraction to assist in separating the organic and aqueous phases. The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated by rotary evaporator to obtain PLC-9.2 as a brown liquid, which was used in the next step without further purification. Full production yield. MS (APCI): Chemical formula: Calculated value of C 21 H 22 F 3 NO 3 ([M+H]+) = 394, experimental value: 394. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.83 (m, 2H ), 7.62 (m, 2H), 7.44 (m, 2H), 7.25 (m, 2H), 4.88 (dd, J = 12.8 Hz, 6.0 Hz, 1H), 4.71 (dd, J = 12.8 Hz, 8.4 Hz, 1H), 4.29 (m, 1H), 3.43 (qd, J = 18.0 Hz, 7.6 Hz, 2H), 2.53 (d, J = 7.2 Hz, 2H), 1.87 (m, 1 H), 0.90 (d, J = 7.8 Hz, 6H),

化合物 PLC-9.3:1-(4-異丁基苯基)-4,4-二甲氧基-3-(4-(三氟甲基)苯基)丁-1-酮:250 mL燒瓶裝配有攪拌棒。向燒瓶中添加化合物 PLC-9.2(2.4 g,6.0 mmol)、THF (67 mL)及MeOH (34 ml)。向溶液中一次性添加KOH (841.7 mg,15.0 mmol)。將溶液在室溫下保持1小時。同時,將H 2SO 4(8 mL)於MeOH (36 mL)中之溶液冷卻至0℃。隨後,在0℃下經由另一漏斗將前述溶液逐滴添加至H 2SO 4溶液中。在添加之後,使反應物升溫至室溫。將反應物在室溫下再保持1小時。LCMS顯示反應完成。將反應溶液傾入碎冰中且用EtOAc (150 ml ×3)萃取。合併之有機相用含10% (w/w) Na 2CO 3之H 2O且隨後用鹽水洗滌。經無水Na 2SO 4乾燥之後,在真空旋轉蒸發儀下濃縮溶液,得到呈棕色油狀物之 PLC-9.3,其不經進一步純化即用於下一步驟。MS (APCI):化學式:C 23H 27F 3O 3([M-OMe]+)之計算值 = 378,實驗值:378。1H NMR (400 MHz, CDCl 2CDCl 2) 7.83 (m, 2H), 7.55 (m, 2H), 7.46 (m, 2H), 7.22 (m, 2H), 4.46 (d, J = 5.2 Hz, 1H), 3.78 (td, J = 9.2 Hz, 5.2 Hz, 1H), 3.54 (dd, J = 17.6 Hz, 4.8 Hz, 1H), 3.39 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.38 (s, 3H), 3.32 (s, 3H), 2.52 (d, J = 7.2 Hz, 1H), 1.88 (m, 1H), 0.90 (d, J = 6.4 Hz, 6H)。 Compound PLC-9.3 : 1-(4-isobutylphenyl)-4,4-dimethoxy-3-(4-(trifluoromethyl)phenyl)butan-1-one: 250 mL flask assembly There is a stir stick. Compound PLC-9.2 (2.4 g, 6.0 mmol), THF (67 mL) and MeOH (34 ml) were added to the flask. KOH (841.7 mg, 15.0 mmol) was added to the solution in one portion. Keep the solution at room temperature for 1 hour. Meanwhile, a solution of H2SO4 (8 mL) in MeOH (36 mL) was cooled to 0° C . Subsequently, the aforementioned solution was added dropwise to the H2SO4 solution via another funnel at 0°C. After addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured into crushed ice and extracted with EtOAc (150 ml × 3). The combined organic phases were washed with 10% (w/w) Na2CO3 in H2O and then brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated on a vacuum rotary evaporator to obtain PLC-9.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Calculated chemical formula: C 23 H 27 F 3 O 3 ([M-OMe]+) = 378, found: 378. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.83 (m, 2H ), 7.55 (m, 2H), 7.46 (m, 2H), 7.22 (m, 2H), 4.46 (d, J = 5.2 Hz, 1H), 3.78 (td, J = 9.2 Hz, 5.2 Hz, 1H), 3.54 (dd, J = 17.6 Hz, 4.8 Hz, 1H), 3.39 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.38 (s, 3H), 3.32 (s, 3H), 2.52 (d, J = 7.2 Hz, 1H), 1.88 (m, 1H), 0.90 (d, J = 6.4 Hz, 6H).

化合物 PLC-9.4 2-(4-異丁基苯基)-4-(4-(三氟甲基)苯基)-1H-吡咯:向100 ml燒瓶中裝入含 PLC-9.3(2.5 g,6.0 mmol)及NH 4•OAc (2.2 g,29.2 mmol)之AcOH (7.2 mL)。在室溫下使溶液脫氣。隨後將其加熱至100℃且在此溫度下保持攪拌5小時。TLC (50% EtOAc/己烷)顯示反應完成。反應混合物藉由添加H 2O (40 mL)淬滅且用DCM (60 mL×3)萃取。合併之有機相用飽和NaHCO 3及鹽水洗滌。經無水Na 2SO 4乾燥之後,在旋轉蒸發儀下濃縮溶液,且藉由矽膠急驟層析使用DCM/己烷(0%-100%)作為溶離劑來純化,得到1.6 g呈淡灰藍色固體狀之純化合物 PLC-9.4,三個步驟之產率78%。MS (APCI):化學式:C 21H 20F 3N ([M-H]-)之計算值 = 343,實驗值:343。1H NMR (400 MHz, CDCl2CDCl2) δ 8.60 (s, 1H), 7.67 (m, 2H), 7.62 (m, 2H), 7.45 (m, 2H), 7.20 (m, 3H), 6.82 (m, 1H), 2.50 (d, J = 7.2 Hz, 1H), 1.89 (m, 1H), 0.93 (d, J = 6.4 Hz, 1H)。 Compound PLC-9.4 : 2-(4-isobutylphenyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole: A 100 ml flask was charged with PLC-9.3 (2.5 g , 6.0 mmol) and NH 4 •OAc (2.2 g, 29.2 mmol) in AcOH (7.2 mL). Degas the solution at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 hours. TLC (50% EtOAc/Hexane) showed the reaction was complete. The reaction mixture was quenched by adding H2O (40 mL) and extracted with DCM (60 mL×3). The combined organic phases were washed with saturated NaHCO 3 and brine. After drying over anhydrous Na 2 SO 4 , the solution was concentrated under a rotary evaporator, and purified by silica gel flash chromatography using DCM/hexane (0%-100%) as the eluent to obtain 1.6 g in light gray blue color. Pure compound PLC-9.4 was obtained as a solid, with a yield of 78% in three steps. MS (APCI): Chemical formula: Calculated value for C 21 H 20 F 3 N ([MH]-) = 343, found value: 343. 1H NMR (400 MHz, CDCl2CDCl2) δ 8.60 (s, 1H), 7.67 (m , 2H), 7.62 (m, 2H), 7.45 (m, 2H), 7.20 (m, 3H), 6.82 (m, 1H), 2.50 (d, J = 7.2 Hz, 1H), 1.89 (m, 1H) , 0.93 (d, J = 6.4 Hz, 1H).

化合物 PLC-9.5 4-(5,5-二氟-3,7-雙(4-異戊基苯基)-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲苯酚:100 mL 2頸圓底燒瓶裝配有空氣冷凝器及攪拌棒。向燒瓶中添加 PLC-9.4(686.8 mg,2.0 mmol)及4-羥基-2,6-二甲基苯甲醛(150.2 mg,1.0 mmol),接著添加無水二氯乙烷(22 mL)。反應混合物用Ar鼓泡30分鐘,隨後添加p-TsOH•H 2O (34.2 mg,0.2 mmol)。將反應溶液加熱至60℃且在此溫度下保持過夜。隨後將反應物冷卻至室溫且添加DDQ (454.0 mg,2.0 mmol)。將反應物在室溫下保持30分鐘。隨後在室溫下添加BF 3•OEt 2(1.5 mL,12.0 mmol)及Et 3N (1.1 mL,8.0 mmol)。將反應混合物加熱至50℃且在此溫度下保持2小時。反應混合物用矽膠負載,且藉由急驟層析使用DCM/己烷(0-100%)作為溶離劑來純化,得到669.0 mg呈深紫藍色固體狀之純 PLC-9.5,77%產率。MS (APCI):化學式:C 51H 45BF 8N 2O ([M-H]-)之計算值 = 864,實驗值:864。1H NMR (400 MHz, CDCl 2CDCl 2) 7.88 (m, 4H), 7.27 (m, 4H), 7.19 (4H), 6.90 (m, 4H), 6.55 (s, 2H), 5.70 (s, 2H), 4.40 (bs, 1H), 2.54 (d, J = 7.2 Hz, 4H), 1.96 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 6.4 Hz, 12H)。 Compound PLC-9.5 : 4-(5,5-difluoro-3,7-bis(4-isopentylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3,5-xylenol: 100 mL The 2-neck round bottom flask is equipped with an air condenser and stirring rod. PLC-9.4 (686.8 mg, 2.0 mmol) and 4-hydroxy-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol) were added to the flask, followed by anhydrous dichloroethane (22 mL). The reaction mixture was bubbled with Ar for 30 min, then p-TsOH·H 2 O (34.2 mg, 0.2 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction was then cooled to room temperature and DDQ (454.0 mg, 2.0 mmol) was added. The reaction was kept at room temperature for 30 minutes. BF 3 •OEt 2 (1.5 mL, 12.0 mmol) and Et 3 N (1.1 mL, 8.0 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and maintained at this temperature for 2 hours. The reaction mixture was supported on silica gel and purified by flash chromatography using DCM/hexane (0-100%) as the eluent to obtain 669.0 mg of pure PLC-9.5 as a deep purple-blue solid, 77% yield. MS (APCI): Chemical formula: Calculated value of C 51 H 45 BF 8 N 2 O ([MH]-) = 864, found value: 864. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 7.88 (m, 4H) , 7.27 (m, 4H), 7.19 (4H), 6.90 (m, 4H), 6.55 (s, 2H), 5.70 (s, 2H), 4.40 (bs, 1H), 2.54 (d, J = 7.2 Hz, 4H), 1.96 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 6.4 Hz, 12H).

化合物 PLC-9:2-(4-(1,3-二側氧基-9-(4-(三氟甲基)苯基)-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加 PLC-9.5(43.2 mg,0.05 mmol)、 PLC-1.5(40.0 mg,0.07 mmol)、DIC (25.2 mg,0.20 mmol)及DMAP•TsOH (29.4 mg,0.10 mmol),接著添加無水DCM (5 ml)。將反應混合物在室溫下保持過夜。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/DCM (0-8%-10%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-9。固體用MeOH (10 ml)進一步濕磨,得到19.0 mg PLC-9,27%產率。MS (APCI):化學式:C 84H 61BF 11N 3O 5([M-H]-)之計算值 = 1411,實驗值:1411。1H NMR (400 MHz, CDCl 2CDCl 2) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.85 (m, 9H), 7.55 (m, 3H), 7.40 (m, 3H), 7.26 (m, 8H), 6.90 (m, 4H), 6.56 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.56 (d, J = 6.8 Hz, 4H), 2.04 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 7.4 Hz, 12H)。 Compound PLC-9 : 2-(4-(1,3-dilateral oxy-9-(4-(trifluoromethyl)phenyl))-1H-xantheno[2,1,9-def]iso Quinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoro) Methyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane-10-yl)-3 ,5-Dimethylphenyl Ester: 25 mL vial equipped with stir bar. Add PLC-9.5 (43.2 mg, 0.05 mmol), PLC-1.5 (40.0 mg, 0.07 mmol), DIC (25.2 mg, 0.20 mmol), and DMAP·TsOH (29.4 mg, 0.10 mmol) to the vial, followed by anhydrous DCM (5ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/DCM (0-8%-10%) as the eluent to obtain pure PLC-9 as a deep purple solid. The solid was further triturated with MeOH (10 ml) to give 19.0 mg of PLC-9 , 27% yield. MS (APCI): Chemical formula: Calculated value of C 84 H 61 BF 11 N 3 O 5 ([MH]-) = 1411, experimental value: 1411. 1H NMR (400 MHz, CDCl 2 CDCl 2 ) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.85 (m, 9H), 7.55 (m, 3H), 7.40 (m, 3H), 7.26 (m, 8H), 6.90 (m, 4H), 6.56 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.56 (d, J = 6.8 Hz, 4H), 2.04 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 7.4 Hz, 12H).

化合物 PLC-10 之合成 Synthesis of compound PLC-10

化合物 PLC-10.1 (6-(4-(三級丁基)-2-硝基苯氧基)-1H,3H-苯并[de]異𠳭烯-1,3-二酮):將1 L 2N圓底燒瓶置放於鋁加熱塊中且向其中裝入攪拌棒。燒瓶裝配有鰭片冷凝器/氣體配接器、塞子及流動控制閥。用氬氣沖洗系統。向燒瓶中添加6-溴-1H,3H-苯并[de]異𠳭烯-1,3-二酮(40.0 mmol,11.084 g)及4-(三級丁基)-2-硝基苯酚(60.0 mmol,11.712 g),接著添加無水NMP (150 mL)。向燒瓶中添加NaOH (20.0 mmol,800 mg)及銅(粉末) (20.0 mmol,1271 mg),接著添加無水NMP (25 mL)。在氬氣氛圍下攪拌燒瓶,其中加熱塊設定為170℃。將反應物在此溫度下攪拌過夜。將反應混合物冷卻至室溫,且用水(175 mL)及1N HCl (44 mL)處理。將反應混合物攪拌30分鐘,隨後濾出,用水洗滌。將沈澱物轉移至具有丙酮/DCM之燒瓶中且蒸發至乾燥,隨後與甲苯共沸。將粗產物溶解於少量DCM中且用甲醇(300 mL)處理。藉由用熱水浴(80℃)旋轉蒸發來移除DCM及一部分甲醇。當所有DCM移除時,將混合物冷卻至室溫且濾出固體。得到8.180 g淺棕色粉末(52%產率)。MS (APCI):化學式:C 22H 17NO 6(M+H)之計算值 = 392;實驗值:392。 1H NMR (400 MHz, 四氯乙烷- d 2) δ 8.82 (dd, J= 8.4, 1.2 Hz, 1H), 8.71 (dd, J= 7.3, 1.2 Hz, 1H), 8.49 (d, J= 8.3 Hz, 1H), 8.16 (d, J= 2.4 Hz, 1H), 7.91 (dd, J= 8.4, 7.3 Hz, 1H), 7.80 (dd, J= 8.6, 2.4 Hz, 1H), 7.34 (d, J= 8.6 Hz, 1H), 6.91 (d, J= 8.3 Hz, 1H), 1.43 (s, 9H)。 Compound PLC-10.1 : (6-(4-(tertiary butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isotriene-1,3-dione): 1 The L 2N round bottom flask was placed in an aluminum heating block and a stirring rod was inserted into it. The flask is equipped with a fin condenser/gas adapter, stopper and flow control valve. Flush the system with argon gas. Add 6-bromo-1H,3H-benzo[de]isotriene-1,3-dione (40.0 mmol, 11.084 g) and 4-(tertiary butyl)-2-nitrophenol ( 60.0 mmol, 11.712 g), followed by anhydrous NMP (150 mL). NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg) were added to the flask, followed by anhydrous NMP (25 mL). The flask was stirred under an argon atmosphere with the heating block set to 170°C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and IN HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered off and washed with water. The precipitate was transferred to a flask with acetone/DCM and evaporated to dryness, then azeotroped with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). DCM and part of the methanol were removed by rotary evaporation using a hot water bath (80°C). When all DCM was removed, the mixture was cooled to room temperature and the solids were filtered off. 8.180 g of light brown powder were obtained (52% yield). MS (APCI): Chemical formula: Calculated value for C 22 H 17 NO 6 (M+H) = 392; Experimental value: 392. 1 H NMR (400 MHz, tetrachloroethane- d 2 ) δ 8.82 (dd, J = 8.4, 1.2 Hz, 1H), 8.71 (dd, J = 7.3, 1.2 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.80 (dd, J = 8.6, 2.4 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 1.43 (s, 9H).

化合物 PLC-10.2 (6-(2-胺基-4-(三級丁基)苯氧基)-1H,3H-苯并[de]異𠳭烯-1,3-二酮):將250 mL 2N圓底燒瓶置放於鋁加熱塊中且向其中裝入攪拌棒。燒瓶裝配有鰭片冷凝器/氣體配接器、塞子及流動控制閥。用氬氣沖洗系統。向燒瓶中添加 PLC-10.1(10.0 mmol,3.914 g)及2-MeTHF (70 mL)。在室溫下攪拌下,添加含HCl之水(100 mmol,4.0N,25 mL)及SnCl 2.2H 2O (40.0 mmol,9.024 g)。將反應混合物在氬氣氛圍下攪拌30分鐘,其中加熱塊設定為90℃。將反應混合物冷卻至0℃,且用2N NaOH水溶液鹼化至pH約8 (pH紙)。濾出固體(緩慢過濾),隨後用2-MeTHF (8 × 100 mL)洗滌所得固體。將濾液轉移至分液漏斗中且分離各層。有機層經MgSO 4乾燥,過濾,且在真空中蒸發至乾燥。得到3.743 g (全收量產率)。其不經進一步純化即用於下一步驟中。MS (APCI):化學式:C 22H 19NO 4(M+H)之計算值 = 362;實驗值:362。 1H NMR (400 MHz, 四氯乙烷- d 2) δ 8.88 (dd, J= 8.4, 1.2 Hz, 1H), 8.69 (dd, J= 7.3, 1.2 Hz, 1H), 8.48 (d, J= 8.4 Hz, 1H), 7.89 (dd, J= 8.4, 7.3 Hz, 1H), 7.03 - 6.93 (m, 3H), 6.88 (dd, J= 8.4, 2.3 Hz, 1H), 1.35 (s, 9H)。 Compound PLC-10.2 : (6-(2-Amino-4-(tertiary butyl)phenoxy)-1H,3H-benzo[de]isotriene-1,3-dione): 250 The mL 2N round bottom flask was placed in an aluminum heating block and a stirring rod was installed into it. The flask is equipped with a fin condenser/gas adapter, stopper and flow control valve. Flush the system with argon gas. Add PLC-10.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL) to the flask. With stirring at room temperature, HCl-containing water (100 mmol, 4.0N, 25 mL) and SnCl 2 .2H 2 O (40.0 mmol, 9.024 g) were added. The reaction mixture was stirred for 30 minutes under an argon atmosphere with the heating block set to 90°C. The reaction mixture was cooled to 0°C and basified to pH ~8 with 2N aqueous NaOH solution (pH paper). The solid was filtered off (slowly) and washed with 2-MeTHF (8 × 100 mL). Transfer the filtrate to a separatory funnel and separate the layers. The organic layer was dried over MgSO4 , filtered, and evaporated in vacuo to dryness. Obtained 3.743 g (full yield). It was used in the next step without further purification. MS (APCI): Chemical formula: Calculated value of C 22 H 19 NO 4 (M+H) = 362; Experimental value: 362. 1 H NMR (400 MHz, tetrachloroethane- d 2 ) δ 8.88 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03 - 6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H).

化合物 PLC-10.3 (9-(三級丁基)-1H,3H-異𠳭烯并[6,5,4-mna]呫噸-1,3-二酮):向40 mL小瓶中裝入攪拌棒、NaNO 2(30.0 mmol,2.070 g)及水(10 mL)。在0℃下在冰水浴中攪拌小瓶。向100 mL圓底燒瓶中裝入攪拌棒及 PLC-10.2(4.00 mmol,1.446 g)。向燒瓶中添加冰AcOH (30 mL)及濃HCl (20.0 mmol,12.1N,1.65 mL)。將混合物在室溫下攪拌幾分鐘,隨後置放於冰水浴中且攪拌約1分鐘。在乙酸開始凍結之前開始添加NaNO 2溶液。經約10分鐘之時段添加NaNO 2。將重氮溶液在0℃下攪拌1小時。在攪拌重氮溶液的同時,準備具有大型攪拌棒之250 mL 2N圓底燒瓶。燒瓶裝配有鰭片冷凝器及滴液漏斗。燒瓶藉由偏心頸部夾持,且將滴液漏斗置放於偏心頸部中,因此溶液將撞擊在攪拌時形成之漩渦之頂部。向此燒瓶中添加CuSO 4.5H 2O (27.4 mmol,6.842 g)及水(80 mL)。在製備重氮溶液前約15分鐘,開始將銅溶液加熱至130℃。當溶液達到130℃時,將重氮溶液轉移至滴液漏斗中,且經約30分鐘之時段在高速攪拌下開始逐滴添加重氮溶液。當添加完成時,將溶液再加熱1至2分鐘,接著在室溫水浴中冷卻。濾出沈澱物,用水洗滌。藉由抽吸乾燥沈澱物,隨後將粗沈澱物溶解/懸浮於DCM中,且在約10 g急驟矽膠上蒸發至乾燥。藉由急驟層析在矽膠(220 g,固體負載,平衡50% DCM/己烷,溶離50% DCM/己烷(2 CV) à 100% DCM (20 CV) à 等度DCM (15 CV) à 0% EtOAc/DCM (0 CV) à 1% EtOAc/DCM (10 CV))上純化。產物位於後部。將含有產物之溶離份在真空中蒸發至乾燥。得到528 mg (38%產率)。MS (APCI):化學式:C 22H 16O 4(M+H)之計算值 = 345;實驗值:345。 1H NMR (400 MHz, 四氯乙烷- d 2) δ 8.61 (d, J= 7.9 Hz, 1H), 8.56 (d, J= 8.4 Hz, 1H), 8.05 (d, J= 2.2 Hz, 1H), 8.01 (d, J= 8.0 Hz, 1H), 7.66 (dd, J= 8.8, 2.2 Hz, 1H), 7.38 (d, J= 8.7 Hz, 1H), 7.34 (d, J= 8.4 Hz, 1H), 1.44 (s, 9H)。 Compound PLC-10.3 : (9-(tertiary butyl)-1H,3H-isotrieno[6,5,4-mna]xanthene-1,3-dione): Fill a 40 mL vial Stir bar, NaNO 2 (30.0 mmol, 2.070 g) and water (10 mL). Stir the vial in an ice water bath at 0°C. Add a stirring rod and PLC-10.2 (4.00 mmol, 1.446 g) to a 100 mL round-bottomed flask. Add ice-cold AcOH (30 mL) and concentrated HCl (20.0 mmol, 12.1N, 1.65 mL) to the flask. The mixture was stirred at room temperature for a few minutes, then placed in an ice-water bath and stirred for about 1 minute. Start adding the NaNO2 solution before the acetic acid starts to freeze. NaNO2 was added over a period of approximately 10 minutes. The diazo solution was stirred at 0°C for 1 hour. While stirring the diazo solution, prepare a 250 mL 2N round-bottomed flask with a large stirring rod. The flask is equipped with a fin condenser and a dropping funnel. The flask is held by an eccentric neck and the dropping funnel is placed in the eccentric neck so that the solution will hit the top of the vortex formed during stirring. To this flask was added CuSO 4 .5H 2 O (27.4 mmol, 6.842 g) and water (80 mL). Approximately 15 minutes before preparing the diazo solution, begin heating the copper solution to 130°C. When the solution reached 130°C, the diazo solution was transferred to the dropping funnel and the diazo solution was added dropwise under high-speed stirring over a period of about 30 minutes. When the addition is complete, the solution is heated for an additional 1 to 2 minutes and then cooled in a room temperature water bath. The precipitate was filtered off and washed with water. The precipitate was dried by aspiration, then the crude precipitate was dissolved/suspended in DCM and evaporated to dryness on ~10 g of flash silica. By flash chromatography on silica gel (220 g, solid loading, equilibration 50% DCM/hexane, dissolution 50% DCM/hexane (2 CV) à 100% DCM (20 CV) à isocratic DCM (15 CV) à Purified on 0% EtOAc/DCM (0 CV) à 1% EtOAc/DCM (10 CV)). The product is located at the rear. The product-containing fractions were evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS (APCI): Chemical formula: Calculated value for C 22 H 16 O 4 (M+H) = 345; Experimental value: 345. 1 H NMR (400 MHz, tetrachloroethane- d 2 ) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 Hz, 1H ), 8.01 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 8.8, 2.2 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H ), 1.44 (s, 9H).

化合物 PLC-10.4 (2-(4-(9-(三級丁基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸)以與 PLC-1.4類似之方式,在無水DMF (10 mL)中由 PLC-10.3(1.191 mmol,410 mg)及2-(4-胺基苯基)乙酸(2.98 mmol,450 mg)合成 PLC-10.4。在處理及沈澱之後,獲得579 mg產物(全收量產率)。MS (APCI):化學式:C 30H 23NO 5(M+H)之計算值 = 478;實驗值:478。 1H NMR (400 MHz, DMSO- d 6) δ 8.48 (d, J= 7.9 Hz, 1H), 8.44 (d, J= 8.3 Hz, 1H), 8.38 (d, J= 8.1 Hz, 1H), 8.27 (d, J= 2.4 Hz, 1H), 7.69 (dd, J= 8.8, 2.3 Hz, 1H), 7.45 - 7.38 (m, 4H), 7.31 - 7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H)。(亦參見化合物PLC-27.2之類似合成,2021年11月12日申請之美國臨時申請案63/278,944) Compound PLC-10.4 : (2-(4-(9-(tertiary butyl)-1,3-bisoxy-1H-xantheno[2,1,9-def]isoquinoline-2( 3H)-yl)phenyl)acetic acid) was prepared from PLC-10.3 (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid in anhydrous DMF (10 mL) in a similar manner to PLC-1.4. (2.98 mmol, 450 mg) Synthesis of PLC-10.4 . After work-up and precipitation, 579 mg of product was obtained (full mass yield). MS (APCI): Chemical formula: Calculated value of C 30 H 23 NO 5 (M+H) = 478; Experimental value: 478. 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.48 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 8.1 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.69 (dd, J = 8.8, 2.3 Hz, 1H), 7.45 - 7.38 (m, 4H), 7.31 - 7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H). (See also similar synthesis of compound PLC-27.2, U.S. Provisional Application 63/278,944 filed on November 12, 2021)

化合物 PLC-10 2-(4-(9-(三級丁基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加 PLC-9.5(60.0 mg,0.07 mmol)、 PLC-10.4(39.8 mg,0.08 mmol)、DIC (35.3 mg,0.28 mmol)及DMAP•TsOH (41.2 mg,0.14 mmol),接著添加無水DCM (6 ml)。將反應混合物在室溫下保持過週末。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/DCM (0-8%-10%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-10。固體用MeOH (19 ml)進一步濕磨,得到26.0 mg PLC-10,28%產率。MS (APCI):化學式:C 81H 66BF 8N 3O 5([M-H] -)之計算值 = 1324,實驗值:1324。 1H NMR (400 MHz, CDCl 2CDCl 2) 8.69 (d, J= 8.0 Hz, 1H), 8.63 (d, J= 8.0 Hz, 1H), 8.09 (d, J= 2.0 Hz, 1H), 8.06 (d, J= 8.0 Hz, 1H), 7.89 (m, 4H), 7.64 (dd, J= 8.8 Hz, 2.4 Hz, 1H), 7.55 (m, 2H), 7.37 (m, 4H), 7.27 (m, 8H), 6.90 (m, 4H), 6.56 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.55 (d, J= 7.2 Hz, 4H), 2.04 (s, 6H), 1.93 (m, 2H), 1.45 (s, 9H), 0.95 (d, J= 7.8 Hz, 12H)。 Compound PLC-10 : 2-(4-(9-(tertiary butyl)-1,3-bisoxy-1H-xantheno[2,1,9-def]isoquinoline-2(3H )-yl)phenyl)acetic acid 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl) -5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethyl Phenyl Ester: 25 mL vial equipped with stir bar. Add PLC-9.5 (60.0 mg, 0.07 mmol), PLC-10.4 (39.8 mg, 0.08 mmol), DIC (35.3 mg, 0.28 mmol), and DMAP·TsOH (41.2 mg, 0.14 mmol) to the vial, followed by anhydrous DCM (6ml). The reaction mixture was kept at room temperature over the weekend. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/DCM (0-8%-10%) as the eluent to obtain pure PLC-10 as a deep purple solid. The solid was further triturated with MeOH (19 ml) to give 26.0 mg of PLC-10 , 28% yield. MS (APCI): Chemical formula: Calculated value of C 81 H 66 BF 8 N 3 O 5 ([MH] - ) = 1324, experimental value: 1324. 1 H NMR (400 MHz, CDCl 2 CDCl 2 ) 8.69 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.09 (d, J = 2.0 Hz, 1H), 8.06 ( d, J = 8.0 Hz, 1H), 7.89 (m, 4H), 7.64 (dd, J = 8.8 Hz, 2.4 Hz, 1H), 7.55 (m, 2H), 7.37 (m, 4H), 7.27 (m, 8H), 6.90 (m, 4H), 6.56 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.55 (d, J = 7.2 Hz, 4H), 2.04 (s, 6H), 1.93 (m, 2H), 1.45 (s, 9H), 0.95 (d, J = 7.8 Hz, 12H).

化合物 PLC-11 之合成 Synthesis of compound PLC-11

化合物 PLC-11 4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-雙(4-(三氟甲基)苯基)-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯基-4-(4-(9-(三級丁基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)丁酸酯:25 mL小瓶裝配有攪拌棒。向小瓶中添加 PLC-9.5(60.0 mg,0.07 mmol)、 PLC-11.1(亦參見 PLC-26.4之類似合成,2021年11月12日申請之美國臨時申請案63/278,944) (42.0 mg,0.08 mmol)、DIC (35.3 mg,0.28 mmol)及DMAP•TsOH (41.2 mg,0.14 mmol),接著添加無水DCM (6 ml)。將反應混合物在室溫下保持過週末。反應混合物用矽膠負載,且藉由急驟層析使用EtOAc/DCM (0-8%-10%)作為溶離劑來純化,得到呈深紫紅色固體狀之純 PLC-11。固體用MeOH (19 ml)進一步濕磨,得到33.0 mg PLC-11,35%產率。MS (APCI):化學式:C 83H 70BF 8N 3O 5([M-H] -)之計算值 = 1352,實驗值:1352。 1H NMR (400 MHz, CDCl 2CDCl 2) 8.67 (d, J= 8.4 Hz, 1H), 8.61 (d, J= 8.4 Hz, 1H), 8.09 (d, J= 2.4 Hz, 1H), 8.06 (d, J= 8.0 Hz, 1H), 7.89 (m, 4H), 7.64 (dd, J= 8.4 Hz, 2.4 Hz, 1H), 7.46 (m, 2H), 7.37 (m, 2H), 7.28 (m, 10H), 6.90 (m, 4H), 6.56 (s, 2H), 6.13 (s, 2H), 2.84 (t, J= 8.0 Hz, 2H), 2.56 (d, J= 7.8 Hz, 4H), 2.55 (m, 2H), 2.11 (m, 2H), 2.03 (s, 6H), 1.92 (m, 2H), 1.45 (s, 9H), 0.94 (d, J= 6.4 Hz, 12H)。 Compound PLC-11 : 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5-dimethylphenyl- 4-(4-(9-(tertiary butyl)-1,3-bisoxy-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)benzene methyl)butyrate: 25 mL vial equipped with stir bar. To the vial, add PLC-9.5 (60.0 mg, 0.07 mmol), PLC-11.1 (see also similar synthesis of PLC-26.4 , U.S. Provisional Application 63/278,944 filed on November 12, 2021) (42.0 mg, 0.08 mmol) ), DIC (35.3 mg, 0.28 mmol) and DMAP·TsOH (41.2 mg, 0.14 mmol), followed by anhydrous DCM (6 ml). The reaction mixture was kept at room temperature over the weekend. The reaction mixture was supported on silica gel and purified by flash chromatography using EtOAc/DCM (0-8%-10%) as the eluent to obtain pure PLC-11 as a deep purple solid. The solid was further triturated with MeOH (19 ml) to give 33.0 mg of PLC-11 in 35% yield. MS (APCI): Chemical formula: Calculated value of C 83 H 70 BF 8 N 3 O 5 ([MH] - ) = 1352, experimental value: 1352. 1 H NMR (400 MHz, CDCl 2 CDCl 2 ) 8.67 (d, J = 8.4 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 2.4 Hz, 1H), 8.06 ( d, J = 8.0 Hz, 1H), 7.89 (m, 4H), 7.64 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.46 (m, 2H), 7.37 (m, 2H), 7.28 (m, 10H), 6.90 (m, 4H), 6.56 (s, 2H), 6.13 (s, 2H), 2.84 (t, J = 8.0 Hz, 2H), 2.56 (d, J = 7.8 Hz, 4H), 2.55 ( m, 2H), 2.11 (m, 2H), 2.03 (s, 6H), 1.92 (m, 2H), 1.45 (s, 9H), 0.94 (d, J = 6.4 Hz, 12H).

化合物 PLC-12 之合成 Synthesis of compound PLC-12

化合物 PLC-12 (2-(4-(5,11-雙(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-(5,5-二氟-3,7-雙(4-異丁基苯基)-1,9-二苯基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-10-基)-3,5-二甲基苯酯):以與 PLC-2類似之方式,在無水DCM (10 mL)中由 PLC-13.6(見下文,0.0823 mmol,70 mg)、 PLC-2.5(0.0549 mmol,40 mg)、DMAP. pTsOH鹽(0.110 mmol,32 mg)及EDC.HCl (0.192 mmol,37 mg)合成 PLC-12。將粗反應混合物用己烷稀釋,且負載至負載器中之約20 g急驟矽膠上。藉由急驟層析在矽膠(120 g,平衡0% EtOAc/DCM,溶離等度0%)上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到62 mg深紅色固體(73%產率)。MS (APCI):化學式:C 91H 64BF 14N 3O 5(M+H)之計算值 = 1556;實驗值:1556。 1H NMR (400 MHz, TCE) δ 8.78 (s, 1H), 8.52 (s, 1H), 8.32 - 8.24 (m, 2H), 8.08 (s, 1H), 8.03 (s, 3H), 7.88 (d, J= 8.0 Hz, 4H), 7.60 (d, J= 8.3 Hz, 2H), 7.49 (ddd, J= 8.5, 6.1, 2.7 Hz, 1H), 7.41 (d, J= 8.3 Hz, 2H), 7.27 (dd, J= 7.8, 4.7 Hz, 5H), 7.07 - 6.88 (m, 8H), 6.78 (dt, J= 6.7, 1.5 Hz, 4H), 6.51 (s, 2H), 6.09 (s, 2H), 3.90 (s, 2H), 2.55 (d, J= 7.1 Hz, 4H), 2.05 (s, 6H), 1.92 (hept, J= 6.6 Hz, 2H), 0.95 (d, J= 6.6 Hz, 12H)。 Compound PLC-12 : (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl))-1,3-dilateral oxy-1H-xantheno[2, 1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9- Diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10-yl)-3,5- Dimethylphenyl ester): In an analogous manner to PLC-2 , in anhydrous DCM (10 mL) from PLC-13.6 (see below, 0.0823 mmol, 70 mg), PLC-2.5 (0.0549 mmol, 40 mg), DMAP. p TsOH salt (0.110 mmol, 32 mg) and EDC.HCl (0.192 mmol, 37 mg) were used to synthesize PLC-12 . The crude reaction mixture was diluted with hexanes and loaded onto approximately 20 g of flash silica in a support vessel. Purified by flash chromatography on silica gel (120 g, equilibration 0% EtOAc/DCM, elution isocratic 0%). The product-containing fractions were evaporated to dryness in vacuo. 62 mg of dark red solid were obtained (73% yield). MS (APCI): Chemical formula: Calculated value of C 91 H 64 BF 14 N 3 O 5 (M+H) = 1556; Experimental value: 1556. 1 H NMR (400 MHz, TCE) δ 8.78 (s, 1H), 8.52 (s, 1H), 8.32 - 8.24 (m, 2H), 8.08 (s, 1H), 8.03 (s, 3H), 7.88 (d , J = 8.0 Hz, 4H), 7.60 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.7 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.27 (dd, J = 7.8, 4.7 Hz, 5H), 7.07 - 6.88 (m, 8H), 6.78 (dt, J = 6.7, 1.5 Hz, 4H), 6.51 (s, 2H), 6.09 (s, 2H), 3.90 (s, 2H), 2.55 (d, J = 7.1 Hz, 4H), 2.05 (s, 6H), 1.92 (hept, J = 6.6 Hz, 2H), 0.95 (d, J = 6.6 Hz, 12H).

化合物 PLC-13 之合成 Synthesis of compound PLC-13

化合物 PLC-13.1 (6-(2-硝基苯氧基)-1H,3H-苯并[de]異𠳭烯-1,3-二酮):將2-硝基苯酚(6.6 g,48 mmol)、KOH粉末(2.4 g,43 mmol)之混合物混合且在真空下攪拌30分鐘,隨後添加銅粉末(0.4 g),接著添加100 mL無水DMF。將混合物攪拌5分鐘,隨後添加4-氯萘二甲酸酐(5.1 g,22 mmol)。使整體脫氣,隨後在回流下加熱1.5小時。冷卻至室溫後,將100 mL 20%鹽酸逐滴添加至所得反應混合物中,使其靜置2小時。藉由過濾收集沈澱物,隨後在真空下乾燥過夜,得到黃棕色固體(4.6 g)。其藉由在回流之乙酸(50 mL)中攪拌1小時而進一步純化,隨後冷卻至室溫。過濾且在空氣中乾燥,得到黃色固體(3.0 g,41%產率)。藉由LCMS (APCI)確認:C 18H 10NO 6(M+H)之計算值:336.0;實驗值:336。 1H NMR (400 MHz, 氯仿- d) δ 8.80 (dd, J= 8.5, 1.2 Hz, 1H), 8.72 (dd, J= 7.3, 1.2 Hz, 1H), 8.50 (d, J= 8.2 Hz, 1H), 8.19 (dd, J= 8.2, 1.7 Hz, 1H), 7.90 (dd, J= 8.5, 7.3 Hz, 1H), 7.79 (td, J= 7.9, 1.7 Hz, 1H), 7.54 (td, J= 8.0, 1.3 Hz, 1H), 7.39 (dd, J= 8.3, 1.2 Hz, 1H), 6.89 (d, J= 8.2 Hz, 1H)。 Compound PLC-13.1 : (6-(2-nitrophenoxy)-1H,3H-benzo[de]isotriene-1,3-dione): 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) were mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 minutes before 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then heated at reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture and allowed to stand for 2 hours. The precipitate was collected by filtration and then dried under vacuum overnight to give a yellow-brown solid (4.6 g). It was further purified by stirring in refluxing acetic acid (50 mL) for 1 hour and then cooled to room temperature. Filtration and drying in air gave a yellow solid (3.0 g, 41% yield). Confirmed by LCMS (APCI): Calculated for C 18 H 10 NO 6 (M+H): 336.0; Found: 336. 1 H NMR (400 MHz, chloroform- d ) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H ), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H).

化合物 PLC-13.2 (6-(2-胺基苯氧基)-1H,3H-苯并[de]異𠳭烯-1,3-二酮):將 PLC-13.1(2.0 g,6 mmol)及鐵粉末(<10 μm,0.91 g,16 mmol)於乙酸(75 mL)中之混合物加熱至回流後保持30分鐘。將所得溶液傾入水(220 mL)中。藉由過濾收集所得沈澱物且用水洗滌,並且在空氣中隨後在真空下徹底乾燥,得到黃色固體(1.65 g,90%產率)。藉由LCMS (APCI)確認:C 18H 12NO 4(M+H)之計算值:306.1;實驗值:306。 Compound PLC-13.2 : (6-(2-aminophenoxy)-1H,3H-benzo[de]isotriene-1,3-dione): PLC-13.1 (2.0 g, 6 mmol) A mixture of iron powder (<10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux and held for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration and washed with water, and dried thoroughly in air and then under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed by LCMS (APCI): Calculated for C 18 H 12 NO 4 (M+H): 306.1; Found: 306.

化合物 PLC-13.3:(1H,3H-異𠳭烯并[6,5,4-mna]呫噸-1,3-二酮): 將 PLC-13.2(1.5 g,4.9 mmol)分散於乙酸(35 mL)中且冷卻至0℃。在攪拌的同時,添加預冷卻之鹽酸(3 mL,37 mmol),隨後在0℃下逐滴添加亞硝酸鈉(3.29 g,46 mmol)於12 mL水中之溶液。將整體在0℃下攪拌一小時,隨後轉移至另一漏斗中,且經一小時時段滴入回流之硫酸銅溶液(5.08 g,20 mmol,於50 mL水中)中。冷卻至室溫後,藉由過濾收集沈澱物,用水及丙酮洗滌,隨後在空氣中接著在真空中乾燥,得到黃色固體(0.92 g,65%產率)。藉由LCMS (APCI)確認:C 18H 8O 4(M-)之計算值:288.0;實驗值:288。 Compound PLC-13.3 : (1H,3H-isotrieno[6,5,4-mna]xanthene-1,3-dione): Disperse PLC-13.2 (1.5 g, 4.9 mmol) in acetic acid (35 mL) and cool to 0°C. While stirring, precooled hydrochloric acid (3 mL, 37 mmol) was added, followed by a solution of sodium nitrite (3.29 g, 46 mmol) in 12 mL of water dropwise at 0°C. The whole was stirred at 0 °C for one hour, then transferred to another funnel and dropped into the refluxing copper sulfate solution (5.08 g, 20 mmol in 50 mL water) over a period of one hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, and then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): Calculated for C 18 H 8 O 4 (M-): 288.0; Found: 288.

化合物 PLC-13.4 (5,11-二溴-1H,3H-異𠳭烯并[6,5,4-mna]呫噸-1,3-二酮):向2 L 2N圓底燒瓶中裝入攪拌棒且裝配有長鰭片冷凝器。向燒瓶中添加 PLC-13.3(34.688 mmol,10.00 g),接著添加鄰二氯苯(1000 mL)。將反應混合物在室溫下攪拌且添加Br 2(416.26 mmol,21.3 mL)。將第二頸塞住,且將反應混合物用鋁加熱塊在75℃下在暴露於空氣的情況下加熱過週末。將反應混合物冷卻至室溫且濾出固體。用己烷(約20%體積)稀釋濾液且濾出第二沈澱物。將此兩份沈澱物在100℃下在真空中乾燥。共10.866 g橙黃色固體(69.9%產率)。兩者具有類似LCMS及NMR。MS (APCI):化學式:C 18H 6Br 2O 4(M+H)之計算值 = 445;實驗值:445。 1H NMR (400 MHz, TCE) δ 9.47 (dd, J= 8.4, 1.5 Hz, 1H), 8.76 (d, J= 14.2 Hz, 2H), 7.72 - 7.63 (m, 1H), 7.56 (dd, J= 8.3, 1.4 Hz, 1H), 7.46 (ddd, J= 8.5, 6.7, 1.9 Hz, 1H)。 Compound PLC-13.4 : (5,11-dibromo-1H,3H-isotrieno[6,5,4-mna]xanthene-1,3-dione): Put into 2 L 2N round bottom flask Insert stirring rod and equipped with long fin condenser. PLC-13.3 (34.688 mmol, 10.00 g) was added to the flask, followed by o-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was plugged and the reaction mixture was heated with an aluminum heating block at 75°C over the weekend with exposure to air. The reaction mixture was cooled to room temperature and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% volume) and the second precipitate was filtered off. The two precipitates were dried in vacuo at 100°C. A total of 10.866 g of orange solid (69.9% yield). Both are similar to LCMS and NMR. MS (APCI): Chemical formula: Calculated value for C 18 H 6 Br 2 O 4 (M+H) = 445; Experimental value: 445. 1 H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).

化合物 PLC-13.5 (2-(4-(5,11-二溴-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸):向100 mL 2N圓底燒瓶中裝入攪拌棒且裝配有鰭片冷凝器/氣體配接器及流動控制件。用氬氣沖洗系統。向燒瓶中添加 PLC-13.4(7.000 mmol,3.136 g)、2-(4-胺基苯基)乙酸(14.00 mmol,2.117 g)、DMAP (2.100 mmol,257 mg)及無水DMF (65 mL)。將反應混合物在設定成160℃之鋁塊中加熱5小時。將粗反應混合物冷卻至0℃且用6N HCl (約5 mL)淬滅,並且用水(至多約350 mL)稀釋。濾出沈澱物,用水洗滌。產物藉由抽吸乾燥且不經進一步純化即用於後續反應中。假定100%產率。MS (APCI):化學式:C 26H 13Br 2NO 5(M+H)之計算值 = 578;實驗值:578。 Compound PLC-13.5 : (2-(4-(5,11-dibromo-1,3-bisoxy-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -(yl)phenyl)acetic acid): A 100 mL 2N round bottom flask was filled with a stir bar and equipped with a fin condenser/gas adapter and flow control. Flush the system with argon gas. Add PLC-13.4 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), DMAP (2.100 mmol, 257 mg) and anhydrous DMF (65 mL) to the flask. The reaction mixture was heated in an aluminum block set to 160°C for 5 hours. The crude reaction mixture was cooled to 0°C and quenched with 6N HCl (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off and washed with water. The product was dried by suction and used in subsequent reactions without further purification. Assuming 100% yield. MS (APCI): Chemical formula: Calculated value for C 26 H 13 Br 2 NO 5 (M+H) = 578; Experimental value: 578.

化合物 PLC-13.6 (2-(4-(5,11-雙(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸):向250 mL 2N圓底燒瓶中裝入攪拌棒且裝配有鰭片冷凝器/氣體配接器及流動控制件。用氬氣沖洗系統。向燒瓶中添加 PLC-13.5(3.500 mmol,2.034 g)、(3,5-雙(三氟甲基)苯基)硼酸(14.00 mmol,3.611)、K 2CO 3(19.25 mmol,2.661 g)、THF (60 mL)、DMF (12 mL)及水(6 mL)。將反應混合物在氬氣下在室溫下攪拌幾分鐘,隨後添加Pd(dppf)Cl 2(0.0245 mmol,179 mg)。頂部空間用氬氣沖洗一分鐘,隨後關閉流動控制件。攪拌反應混合物,且在80℃之鋁加熱塊中加熱三小時。將粗反應混合物在真空中蒸發至乾燥,溶解於DCM中,且在真空中蒸發至約35 g急驟矽膠上。藉由急驟層析在矽膠(220 g,平衡0% EtOAc/DCM,溶離0% (10 CV) à 15.3% EtOAc/DCM (15.3 CV) à 40% EtOAc/DCM (10 CV) à 等度40% EtOAc/DCM)上純化。EtOAc含有0.1% v/v TFA。得到1.710 g褐黃色固體(57.6%產率)。MS (APCI):化學式:C 42H 19F 12NO 5(M+H)之計算值 = 846;實驗值:846。 1H NMR (400 MHz, DMSO) δ 12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J= 1.7 Hz, 2H), 8.36 (s, 1H), 8.30 (s, 1H), 8.26 (d, J= 1.6 Hz, 2H), 8.24 (s, 1H), 7.50 (ddd, J= 8.5, 7.2, 1.5 Hz, 1H), 7.46 - 7.38 (m, 2H), 7.37 - 7.27 (m, 2H), 7.14 (dd, J= 8.3, 1.2 Hz, 1H), 6.98 (ddd, J= 8.4, 7.2, 1.3 Hz, 1H), 6.85 (dd, J= 8.3, 1.5 Hz, 1H), 3.69 (s, 2H)。 Compound PLC-13.6 : (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl))-1,3-dilateral oxy-1H-xantheno[2, 1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Into a 250 mL 2N round bottom flask equipped with a stir bar and equipped with fin condenser/gas adapter and flow control pieces. Flush the system with argon gas. Add PLC-13.5 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611), K 2 CO 3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL) and water (6 mL). The reaction mixture was stirred at room temperature under argon for a few minutes before Pd(dppf) Cl2 (0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for one minute and the flow control was subsequently closed. The reaction mixture was stirred and heated in an aluminum heating block at 80°C for three hours. The crude reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, and evaporated in vacuo to approximately 35 g of flash silica. By flash chromatography on silica gel (220 g, equilibrated 0% EtOAc/DCM, elution 0% (10 CV) à 15.3% EtOAc/DCM (15.3 CV) à 40% EtOAc/DCM (10 CV) à isocratic 40% EtOAc/DCM). EtOAc contains 0.1% v/v TFA. 1.710 g of tan solid were obtained (57.6% yield). MS (APCI): Chemical formula: Calculated value of C 42 H 19 F 12 NO 5 (M+H) = 846; Experimental value: 846. 1 H NMR (400 MHz, DMSO) δ 12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J = 1.7 Hz, 2H), 8.36 (s, 1H), 8.30 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 7.50 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.46 - 7.38 (m, 2H), 7.37 - 7.27 (m, 2H), 7.14 (dd, J = 8.3, 1.2 Hz, 1H), 6.98 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.85 (dd, J = 8.3, 1.5 Hz, 1H), 3.69 (s , 2H).

化合物 PLC-13 (10-(4-(2-(4-(5,11-雙(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙醯氧基)-2,6-二甲基苯基)-5,5-二氟-1,3,7,9-四甲基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-2,8-二甲酸二乙酯):將 PLC-13.6(0.113 mmol,80 mg)、 PLC-13.7(5,5-二氟-10-(4-羥基-2,6-二甲基苯基)-1,3,7,9-四甲基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-2,8-二甲酸二乙酯,如WO2021188392 A1中所描述合成,0.0750 mmol,38 mg)及DMAP. pTsOH鹽(0.150 mmol,44 mg)放入具有攪拌棒之40 mL螺帽小瓶中。向小瓶中添加無水DCM (10 mL)且攪拌混合物,得到溶液。向小瓶中添加DIC (0.263 mmol,0.41 mL)。將反應物加蓋,且在室溫下攪拌過夜。將粗反應混合物用己烷稀釋,且負載至負載器中之約20 g急驟矽膠上。藉由急驟層析在矽膠(120 g,平衡0% EtOAc/己烷,溶離0% (2 CV) à 50% EtOAc/己烷(30 CV))上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到70 mg橙色固體(78%產率)。MS (APCI):化學式:C 65H 46BF 8N 3O 9(M+H)之計算值 = 1176;實驗值:1176。 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.80 (m, 6H), 7.66 (t, J= 8.4 Hz, 4H), 7.47 - 7.35 (m, 3H), 7.31 (dd, J= 8.3, 1.3 Hz, 1H), 7.10 (dd, J= 8.4, 1.5 Hz, 1H), 7.05 (s, 2H), 6.96 (ddd, J= 8.4, 7.1, 1.4 Hz, 1H), 4.28 (q, J= 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.15 (s, 6H), 1.73 (s, 6H), 1.34 (t, J= 7.1 Hz, 6H)。 Compound PLC-13 : (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl))-1,3-dilateral oxy-1H- Xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetyloxy)-2,6-dimethylphenyl)-5,5-difluoro- 1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane-2 ,8-Diethyl dicarboxylate): Combine PLC-13.6 (0.113 mmol, 80 mg), PLC-13.7 (5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl) -1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane- Diethyl 2,8-dicarboxylate, synthesized as described in WO2021188392 A1, 0.0750 mmol, 38 mg) and DMAP.p TsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw cap vial with a stirring rod. Anhydrous DCM (10 mL) was added to the vial and the mixture was stirred to obtain a solution. Add DIC (0.263 mmol, 0.41 mL) to the vial. The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexanes and loaded onto approximately 20 g of flash silica in a support vessel. Purified by flash chromatography on silica gel (120 g, equilibration 0% EtOAc/hexanes, elution 0% (2 CV) à 50% EtOAc/hexanes (30 CV)). The product-containing fractions were evaporated to dryness in vacuo. 70 mg of orange solid were obtained (78% yield). MS (APCI): Chemical formula: Calculated value of C 65 H 46 BF 8 N 3 O 9 (M+H) = 1176; Experimental value: 1176. 1 H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.80 (m, 6H), 7.66 (t, J = 8.4 Hz, 4H), 7.47 - 7.35 (m , 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.05 (s, 2H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.15 (s, 6H), 1.73 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).

化合物 PLC-14 之合成 Synthesis of compound PLC-14

化合物 PLC-14.1 (2-(4-(5,11-雙(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙酸4-甲醯基-3,5-二甲基苯酯):藉由將含 PLC-13.6(0.150 mmol,127 mg)、4-羥基-2,6-二甲基苯甲醛(0.450 mmol,68 mg)、DMAP. pTsOH鹽(0.300 mmol,88 mg)及EDC.HCl (0.525 mmol,101 mg)之無水二氯甲烷(20 mL)在室溫下攪拌過夜來合成 PLC-14.1。將粗反應混合物負載至負載器中之約25 g急驟矽膠上。藉由急驟層析在矽膠(80 g,平衡0% EtOAc/己烷,溶離0% (2 CV) à 50% EtOAc/EtOAc (20 CV))上純化。NMR顯示約40 mol% 4-羥基-2,6-二甲基苯甲醛。按原樣用於下一步驟中。得到120 mg黃色固體(81%產率)。MS (APCI):化學式:C 51H 27F 12NO 6(M+H)之計算值 = 978;實驗值:978。 1H NMR (400 MHz, TCE) δ 10.55 (s, 1H), 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (d, J= 1.6 Hz, 2H), 8.07 (s, 1H), 8.03 (t, J= 2.3 Hz, 3H), 7.65 - 7.57 (m, 2H), 7.49 (ddd, J= 8.6, 6.1, 2.6 Hz, 1H), 7.41 - 7.35 (m, 2H), 7.31 - 7.23 (m, 1H), 7.05 - 6.95 (m, 2H), 6.92 (s, 2H), 4.01 (s, 2H), 2.62 (s, 6H)。 Compound PLC-14.1 : (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl))-1,3-dilateral oxy-1H-xantheno[2, 1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 4-formyl-3,5-dimethylphenyl ester): by adding PLC-13.6 (0.150 mmol, 127 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (0.450 mmol, 68 mg), DMAP.p TsOH salt (0.300 mmol, 88 mg) and EDC.HCl (0.525 mmol, 101 mg) anhydrous Methyl chloride (20 mL) was stirred at room temperature overnight to synthesize PLC-14.1 . Load the crude reaction mixture onto approximately 25 g of flash silica in a support vessel. Purified by flash chromatography on silica gel (80 g, equilibration 0% EtOAc/Hexane, elution 0% (2 CV) à 50% EtOAc/EtOAc (20 CV)). NMR showed approximately 40 mol% 4-hydroxy-2,6-dimethylbenzaldehyde. Use as is in the next step. 120 mg of yellow solid were obtained (81% yield). MS (APCI): Chemical formula: Calculated value of C 51 H 27 F 12 NO 6 (M+H) = 978; Experimental value: 978. 1 H NMR (400 MHz, TCE) δ 10.55 (s, 1H), 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (d, J = 1.6 Hz, 2H), 8.07 (s, 1H), 8.03 (t, J = 2.3 Hz, 3H), 7.65 - 7.57 (m, 2H), 7.49 (ddd, J = 8.6, 6.1, 2.6 Hz, 1H), 7.41 - 7.35 (m, 2H), 7.31 - 7.23 ( m, 1H), 7.05 - 6.95 (m, 2H), 6.92 (s, 2H), 4.01 (s, 2H), 2.62 (s, 6H).

化合物 PLC-14 (10-(4-(2-(4-(5,11-雙(3,5-雙(三氟甲基)苯基)-1,3-二側氧基-1H-呫噸并[2,1,9-def]異喹啉-2(3H)-基)苯基)乙醯氧基)-2,6-二甲基苯基)-5,5-二氟-3,7-二甲基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼烷-2,8-二甲酸二乙酯):向100 mL 2N圓底燒瓶中裝入攪拌棒且裝配有鰭片冷凝器/氣體配接器及流動控制件,且將其置放於鋁加熱塊中。用氬氣沖洗系統。向燒瓶中添加 PLC-14.1(0.289 mmol,120 mg)、2-甲基-1H-吡咯-3-甲酸乙酯(0.578 mmol,87 mg)及無水DCE (20 mL)。在室溫下攪拌系統,且頂部空間用氬氣沖洗30秒,隨後添加 pTsOH.H 2O (0.0868 mmol,16 mg)。將頂部空間再沖洗30秒,隨後將系統封閉且在氬氣下攪拌。將反應混合物在50℃下加熱且攪拌過夜。將反應混合物冷卻至室溫且添加DDQ (0.492 mmol,111 mg)。將反應物在室溫下攪拌30分鐘,隨後添加Et 3N (2.313 mmol,0.32 mL)及BF 3.OEt 2(3.468 mmol,0.43 mL)。在1分鐘內,重複添加Et 3N (2.313 mmol,0.32 mL)及BF 3.OEt 2(3.468 mmol,0.43 mL)。將反應物加熱至50℃且攪拌一小時。將粗反應混合物在減壓下蒸發以移除大部分DCE,隨後負載至負載器中之約25 g急驟矽膠上。藉由急驟層析在矽膠(120 g,平衡0% EtOAc/甲苯,溶離0% (2 CV) à 10% EtOAc/甲苯(60 CV))上純化。將含有產物之溶離份在真空中蒸發至乾燥。得到106 mg橙色固體(66%產率)。MS (APCI):化學式:C 67H 44BF 14N 3O 9(M+H)之計算值 = 1312;實驗值:1312。 1H NMR (400 MHz, TCE) δ 8.77 (s, 1H), 8.51 (s, 1H), 8.29 - 8.25 (m, 2H), 8.07 (s, 1H), 8.03 (d, J= 1.9 Hz, 3H), 7.70 - 7.61 (m, 2H), 7.49 (ddd, J= 8.5, 5.9, 2.8 Hz, 1H), 7.43 - 7.36 (m, 2H), 7.32 - 7.24 (m, 1H), 7.08 (s, 2H), 7.05 - 6.95 (m, 4H), 4.26 (q, J= 7.1 Hz, 4H), 4.04 (s, 2H), 2.93 (s, 6H), 2.17 (s, 6H), 1.32 (t, J= 7.1 Hz, 6H)。 Compound PLC-14 : (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl))-1,3-dilateral oxy-1H- Xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetyloxy)-2,6-dimethylphenyl)-5,5-difluoro- 3,7-Dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborane-2,8-di Diethyl formate): A 100 mL 2N round bottom flask equipped with a stir bar and equipped with a fin condenser/gas adapter and flow control was placed in an aluminum heating block. Flush the system with argon gas. To the flask was added PLC-14.1 (0.289 mmol, 120 mg), 2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester (0.578 mmol, 87 mg) and anhydrous DCE (20 mL). The system was stirred at room temperature and the headspace was flushed with argon for 30 seconds before pTsOH.H2O (0.0868 mmol, 16 mg) was added. The headspace was flushed for an additional 30 seconds before the system was closed and stirred under argon. The reaction mixture was heated at 50°C and stirred overnight. The reaction mixture was cooled to room temperature and DDQ (0.492 mmol, 111 mg) was added. The reaction was stirred at room temperature for 30 minutes before Et3N (2.313 mmol, 0.32 mL) and BF3.OEt2 ( 3.468 mmol, 0.43 mL) were added. Within 1 minute, Et3N (2.313 mmol, 0.32 mL) and BF3.OEt2 (3.468 mmol , 0.43 mL) were added repeatedly. The reaction was heated to 50°C and stirred for one hour. The crude reaction mixture was evaporated under reduced pressure to remove most of the DCE and then loaded onto approximately 25 g of flash silica in a support. Purified by flash chromatography on silica gel (120 g, equilibration 0% EtOAc/toluene, dissolution 0% (2 CV) à 10% EtOAc/toluene (60 CV)). The product-containing fractions were evaporated to dryness in vacuo. 106 mg of orange solid were obtained (66% yield). MS (APCI): Chemical formula: Calculated value of C 67 H 44 BF 14 N 3 O 9 (M+H) = 1312; Experimental value: 1312. 1 H NMR (400 MHz, TCE) δ 8.77 (s, 1H), 8.51 (s, 1H), 8.29 - 8.25 (m, 2H), 8.07 (s, 1H), 8.03 (d, J = 1.9 Hz, 3H ), 7.70 - 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 5.9, 2.8 Hz, 1H), 7.43 - 7.36 (m, 2H), 7.32 - 7.24 (m, 1H), 7.08 (s, 2H ), 7.05 - 6.95 (m, 4H), 4.26 (q, J = 7.1 Hz, 4H), 4.04 (s, 2H), 2.93 (s, 6H), 2.17 (s, 6H), 1.32 (t, J = 7.1 Hz, 6H).

實例 3 製造薄膜以用於光學性質評估大體上以以下方式製備玻璃基板。將1.1 mm厚的玻璃基板切割成1吋×1吋之尺寸。隨後將玻璃基板用清潔劑及去離子(DI)水洗滌,用新制DI水沖洗,且超音波處理約1小時。隨後將玻璃浸泡於異丙醇(IPA)中且用超音波處理約1小時。隨後將玻璃基板浸泡於丙酮中且用超音波處理約1小時。隨後自丙酮浴中移出玻璃且在氮氣下在室溫下乾燥。 Example 3 Fabrication of Thin Films for Optical Property Evaluation A glass substrate was prepared generally in the following manner. Cut the 1.1 mm thick glass substrate into 1 inch × 1 inch size. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with freshly prepared DI water, and ultrasonic treated for about 1 hour. The glass was then soaked in isopropyl alcohol (IPA) and ultrasonicated for approximately 1 hour. The glass substrate was then soaked in acetone and ultrasonicated for about 1 hour. The glass was then removed from the acetone bath and dried under nitrogen at room temperature.

製備聚(甲基丙烯酸甲酯) (PMMA) (藉由GPC量測之平均分子量為120,000,來自MilliporeSigma, Burlington, MA, USA)聚合物於甲苯中之25 wt%溶液。將製備的含PMMA聚合物之甲苯在60℃下攪拌過夜直至完全溶解。[PMMA] CAS:9011-14-7;[甲苯] CAS:108-88-3。A 25 wt% solution of poly(methyl methacrylate) (PMMA) (average molecular weight by GPC 120,000, from MilliporeSigma, Burlington, MA, USA) polymer in toluene was prepared. The prepared PMMA polymer-containing toluene was stirred at 60° C. overnight until completely dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.

在密封容器中,將上文所製備的25% PMMA溶液(3.4 mL)添加至如上文所描述製備的2 mg發色團染料中,且使用渦旋充分混合5分鐘,並且用超音波處理30分鐘。隨後以1000 RPM將PMMA/發色團溶液旋塗於所製備之玻璃基板上,持續20秒。所得濕塗層之厚度為約10 µm。三個樣品各自以此方式製備以用於吸收、發射/FWHM及量子產率量測。將旋塗之樣品在烘箱中在150℃下烘烤5分鐘以使剩餘溶劑蒸發。在PMMA中製備之PLC-1及PLC-2之資料展示於下方表2及表3中。亦在聚(丙烯酸丁酯) (PBA)中製備PLC-1及PLC-2,其中使用PBA溶液代替PMMA溶液。聚(丙烯酸丁酯) (PBA)溶液(藉由GPC量測之平均分子量為約99,000)係購自Sigma Aldrich,CAS:9003-49-0。在PBA中製備之PLC-1及PLC-2之資料展示於下方表2及表3中。In a sealed container, add the 25% PMMA solution (3.4 mL) prepared above to the 2 mg chromophore dye prepared as described above and mix well using a vortex for 5 min and sonicate for 30 minute. The PMMA/chromophore solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds. The thickness of the resulting wet coating was approximately 10 µm. Three samples were each prepared in this manner for absorption, emission/FWHM and quantum yield measurements. The spin-coated samples were baked in an oven at 150°C for 5 minutes to evaporate the remaining solvent. Data for PLC-1 and PLC-2 prepared in PMMA are shown in Tables 2 and 3 below. PLC-1 and PLC-2 were also prepared in poly(butyl acrylate) (PBA), using PBA solution instead of PMMA solution. Poly(butyl acrylate) (PBA) solution (average molecular weight as measured by GPC was approximately 99,000) was purchased from Sigma Aldrich, CAS: 9003-49-0. Data for PLC-1 and PLC-2 prepared in PBA are shown in Tables 2 and 3 below.

對於吸收光譜量測,將1吋×1吋樣品插入Shimadzu UV-3600 UV-VIS-NIR分光光度計(Shimadzu Instruments, Inc., Columbia, MD, USA)中。For absorption spectrum measurements, 1 inch × 1 inch samples were inserted into a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA).

如上文所描述製備之1吋×1吋膜樣品之螢光光譜係使用Fluorolog分光螢光計(Horiba Scientific, Edison, NJ, USA)測定,其中激發波長設定為各別最大吸收波長。最大發射及FWHM展示於表1中。The fluorescence spectra of 1 inch × 1 inch film samples prepared as described above were measured using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set to the respective maximum absorption wavelength. Maximum emission and FWHM are shown in Table 1.

PLC-1之所得吸收/發射光譜展示於 1中。PLC-2之所得吸收/發射光譜展示於 2中。 The resulting absorption/emission spectrum of PLC-1 is shown in Figure 1 . The resulting absorption/emission spectrum of PLC-2 is shown in Figure 2 .

如上文所描述製備之1吋×1吋樣品之量子產率係藉由Hamamatsu C11347絕對PL量子產率光譜儀(Hamamatsu Inc., Campbell CA, USA)測定。自390 nm至450 nm (作為激發波長)每30 nm掃描波長以用於量子產率量測。自玻璃中取出0.5"×0.5"大小之膜以用於量測。450 nm下之QY結果報告於表1中。The quantum yield of 1 inch x 1 inch samples prepared as described above was measured by a Hamamatsu C11347 absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). Wavelengths were scanned every 30 nm from 390 nm to 450 nm (as excitation wavelength) for quantum yield measurements. Remove a 0.5" x 0.5" film from the glass for measurement. QY results at 450 nm are reported in Table 1.

如上文所描述製備之1吋×1吋膜樣品之螢光光譜係使用Fluorolog分光螢光計(Horiba Scientific, Edison, NJ, USA)測定,其中激發波長設定為各別最大吸收波長。最大發射及FWHM展示於表1中。The fluorescence spectra of 1 inch × 1 inch film samples prepared as described above were measured using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set to the respective maximum absorption wavelength. Maximum emission and FWHM are shown in Table 1.

如上文所描述製備之1吋×1吋樣品之量子產率係使用Quantarus-QY分光光度計(Hamamatsu Inc., Campbell CA, USA)測定,在各別最大吸收波長下激發。結果報告於表1中。Quantum yields of 1" x 1" samples prepared as described above were measured using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA), excited at respective maximum absorption wavelengths. The results are reported in Table 1.

膜表徵(吸收峰值波長、FWHM及量子產率)之結果展示於表1中。 1. 化合物 結構 發射(nm) FWHM (nm) 450 nm 激發下之QY CE-1 512 24 <1% CE-2 592 37 <1% 化合物 結構 PMMA中之吸收(nm) PMMA中之發射(nm) FWHM (nm) QY (在450 nm下) PLC-1 568 600 38 89% PLC-3 568 601 38 89.7% PLC-2 574 606 37 90.5% PLC-4 574 604 37 90.4% PLC-5 571 602 38 90.8% PLC-6 571 604 38 89.3% PLC-7 571 603 36 91.1% PLC-8 575 608 38 91.2% PLC-9 576 610 40 89.9% PLC-10 578 610 38 90.0% PLC-11 578 610 39 89.9% PLC-12 574 606 38 91% PLC-13 503 513 23 92% PLC-14 513 522 22 92% The results of film characterization (absorption peak wavelength, FWHM and quantum yield) are shown in Table 1. Table 1. compound structure Emission(nm) FWHM (nm) QY under 450 nm excitation CE-1 512 twenty four <1% CE-2 592 37 <1% compound structure Absorption in PMMA (nm) Emission in PMMA (nm) FWHM (nm) QY (at 450 nm) PLC-1 568 600 38 89% PLC-3 568 601 38 89.7% PLC-2 574 606 37 90.5% PLC-4 574 604 37 90.4% PLC-5 571 602 38 90.8% PLC-6 571 604 38 89.3% PLC-7 571 603 36 91.1% PLC-8 575 608 38 91.2% PLC-9 576 610 40 89.9% PLC-10 578 610 38 90.0% PLC-11 578 610 39 89.9% PLC-12 574 606 38 91% PLC-13 503 513 twenty three 92% PLC-14 513 522 twenty two 92%

另外,如上文所描述之PMMA膜及PBA/AA膜之量子產率結果提供於下方表2及表3中: 2 PLC-1 PMMA PBA/AA QY% (450) 0.89 0.800 QY% (390) 0.876 0.702 3 PLC-2 PMMA PBA/AA QY% (450) 0.905 0.844 QY% (390) 0.903 0.758 Additionally, quantum yield results for PMMA films and PBA/AA films as described above are provided in Tables 2 and 3 below: Table 2 PLC-1 PMMA PBA/AA QY% (450) 0.89 0.800 QY% (390) 0.876 0.702 table 3 PLC-2 PMMA PBA/AA QY% (450) 0.905 0.844 QY% (390) 0.903 0.758

相關申請案之交互參考本申請案主張2022年2月18日申請之美國臨時申請案第63/311,579號及2022年10月14日申請之美國臨時申請案第63/379,583號之優先權,兩者均以全文引用之方式併入。 Cross-Reference to Related Applications This application claims priority to U.S. Provisional Application No. 63/311,579, filed on February 18, 2022, and U.S. Provisional Application No. 63/379,583, filed on October 14, 2022. All are incorporated by reference in full.

1為描繪光致發光複合物之一個實施例(PLC-1)之吸收及發射光譜的曲線圖。 2為描繪光致發光複合物之一個實施例(PLC-2)之吸收及發射光譜的曲線圖。 Figure 1 is a graph depicting the absorption and emission spectra of one embodiment of the photoluminescent composite (PLC-1). Figure 2 is a graph depicting the absorption and emission spectra of one embodiment of the photoluminescent composite (PLC-2).

Claims (21)

一種光致發光複合物,其包含: 吸收藍光之呫噸并異喹啉衍生物; 連接子複合物,其中該連接子複合物為未經取代之酯或經取代之酯;及 硼-二吡咯亞甲基(BODIPY)部分; 其中該連接子複合物共價連接該呫噸并異喹啉衍生物與該BODIPY部分,其中該呫噸并異喹啉衍生物吸收第一激發波長之光能且將能量傳遞至該BODIPY部分,其中該BODIPY部分吸收來自該呫噸并異喹啉衍生物之該能量且發射第二較高波長之光能,且其中該光致發光複合物具有大於80%之發射量子產率。 A photoluminescent compound containing: Xanthenoisoquinoline derivatives that absorb blue light; a linker complex, wherein the linker complex is an unsubstituted ester or a substituted ester; and Boron-dipyrromethene (BODIPY) moiety; wherein the linker complex covalently connects the xanthenoisoquinoline derivative and the BODIPY moiety, wherein the xanthenoisoquinoline derivative absorbs light energy of the first excitation wavelength and transfers energy to the BODIPY moiety, wherein the BODIPY partially absorbs the energy from the xanthenoisoquinoline derivative and emits light energy of a second higher wavelength, and wherein the photoluminescent composite has an emission quantum yield greater than 80%. 如請求項1之光致發光複合物,其中該呫噸并異喹啉衍生物具有以下通式: ,其中R 9為H或視情況經取代之芳基,且R 10為H、C 1-C 4烷基或視情況經取代之芳基。 The photoluminescent composite of claim 1, wherein the xanthenoisoquinoline derivative has the following general formula: , wherein R 9 is H or optionally substituted aryl, and R 10 is H, C 1 -C 4 alkyl or optionally substituted aryl. 如請求項2之光致發光複合物,其中該視情況經取代之芳基包含 The photoluminescent compound of claim 2, wherein the optionally substituted aryl group includes . 如請求項1之光致發光複合物,其中該BODIPY部分具有以下通式: 其中R 1、R 2、R 3、R 4、R 5、R 6獨立地為H、C 1-C 3烷基、芳基、酯或醚;且 其中R 7及R 8獨立地為H或甲基(-CH 3);且 其中L為連接子複合物,其包含未經取代之酯或經取代之酯。 The photoluminescent composite of claim 1, wherein the BODIPY part has the following general formula: Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently H, C 1 -C 3 alkyl, aryl, ester or ether; and wherein R 7 and R 8 are independently H or Methyl (-CH 3 ); and wherein L is a linker complex comprising an unsubstituted ester or a substituted ester. 如請求項4之光致發光複合物,其中R 3及R 4獨立地為H、甲基或視情況經取代之芳基。 The photoluminescent compound of claim 4, wherein R 3 and R 4 are independently H, methyl or optionally substituted aryl. 如請求項6之光致發光複合物,其中該視情況經取代之芳基包含 The photoluminescent compound of claim 6, wherein the optionally substituted aryl group includes . 如請求項4之光致發光複合物,其中R 2及R 5為酯。 The photoluminescent compound of claim 4, wherein R 2 and R 5 are esters. 如請求項7之光致發光複合物,其中該酯為 The photoluminescent compound of claim 7, wherein the ester is . 如請求項1之光致發光複合物,其中該連接子複合物為經取代之酯,其包含: The photoluminescent complex of claim 1, wherein the linker complex is a substituted ester comprising: . 如請求項1之光致發光複合物,其中該連接子複合物為未經取代之酯,其包含: The photoluminescent complex of claim 1, wherein the linker complex is an unsubstituted ester, which includes: . 如請求項1、2、3、4、5、6、7、8、9或10之光致發光複合物,其中該連接子複合物之該經取代之酯為 The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the substituted ester of the linker complex is or . 如請求項1之光致發光複合物,其中該光致發光複合物包含: 或其組合。 The photoluminescent compound of claim 1, wherein the photoluminescent compound contains: or combination thereof. 一種色轉換膜,其包含: 透明基板層; 色轉換層,其中該色轉換層包括樹脂基質;及 光致發光複合物,其分散於該樹脂基質內,其中該光致發光複合物包含如請求項1、2、3、4、5、6、7、8、9、10、11或12之光致發光化合物。 A color conversion film containing: Transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix; and Photoluminescent composite dispersed in the resin matrix, wherein the photoluminescent composite contains light as claimed in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 Luminescent compounds. 如請求項13之色轉換膜,其中該樹脂基質包含聚(甲基丙烯酸甲酯)。The color conversion film of claim 13, wherein the resin matrix includes poly(methyl methacrylate). 如請求項13之色轉換膜,其中該樹脂基質包含聚(丙烯酸丁酯)。The color conversion film of claim 13, wherein the resin matrix includes poly(butyl acrylate). 如請求項13之色轉換膜,其中該膜之厚度在10 μm與200 μm之間。The color conversion film of claim 13, wherein the thickness of the film is between 10 μm and 200 μm. 如請求項13之色轉換膜,其中該膜吸收約400 nm至約480 nm波長範圍內之光且發射575 nm至約645 nm波長範圍內之光。The color conversion film of claim 13, wherein the film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of 575 nm to about 645 nm. 一種用於製備色轉換膜之方法,該方法包含: 將如請求項1、2、3、4、5、6、7、8、9、10、11或12之光致發光複合物及黏合劑樹脂溶解於溶劑內;及 將該混合物塗覆至透明基板相對表面中之一者。 A method for preparing a color conversion film, the method comprising: Dissolve the photoluminescent composite and binder resin as claimed in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 in a solvent; and The mixture is applied to one of the opposing surfaces of the transparent substrate. 如請求項18之方法,其中該黏合劑樹脂包含聚(丙烯酸丁酯)。The method of claim 18, wherein the adhesive resin includes poly(butyl acrylate). 一種背光單元,其包含如請求項13、14、15、16或17之色轉換膜。A backlight unit comprising the color conversion film of claim 13, 14, 15, 16 or 17. 一種顯示裝置,其包含如請求項20之背光單元。A display device including the backlight unit of claim 20.
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