Nothing Special   »   [go: up one dir, main page]

TWI785816B - 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof - Google Patents

11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof Download PDF

Info

Publication number
TWI785816B
TWI785816B TW110135685A TW110135685A TWI785816B TW I785816 B TWI785816 B TW I785816B TW 110135685 A TW110135685 A TW 110135685A TW 110135685 A TW110135685 A TW 110135685A TW I785816 B TWI785816 B TW I785816B
Authority
TW
Taiwan
Prior art keywords
phenanthridin
carbonyl
formula
tetrahydrofuran
methoxy
Prior art date
Application number
TW110135685A
Other languages
Chinese (zh)
Other versions
TW202200578A (en
Inventor
莊士卿
賈亞庫馬 賈亞尚德倫
Original Assignee
國立陽明交通大學
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 國立陽明交通大學 filed Critical 國立陽明交通大學
Priority to TW110135685A priority Critical patent/TWI785816B/en
Publication of TW202200578A publication Critical patent/TW202200578A/en
Application granted granted Critical
Publication of TWI785816B publication Critical patent/TWI785816B/en

Links

Images

Landscapes

  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Herein, a highly regioselective synthesis of 11-arylcinnolino[2,3-f ]phenanthridin-9-ium salts from 2-azobiaryls and alkenes catalyzed by palladium is demonstrated. The reaction proceeds through double oxidative C-H coupling of alkenes, giving moderate yields of polycyclic cinnolinium salts. The reaction mechanism is proposed involving anortho C-H olefination of 2-azobiaryls by alkenes, intramolecular aza-Michael addition, β-hydride elimination, electrophilic palladation followed by intramolecular C-H activation and reductive elimination.

Description

11-芳香基噌啉[2,3-f]菲啶鹽化合物及其製造方法11-aryl cinnolin [2,3-f] phenanthridine salt compound and its production method

本發明係關於11-芳香基噌啉[2,3-f]菲啶鹽化合物及其製造方法。The present invention relates to 11-aryl cinnolin [2,3-f] phenanthridine salt compound and its production method.

噌啉鹽類在有機光電材料的應用日漸受到矚目，尤其是當中具有高分子量及在有機溶劑中具有良好的溶解性者，具有高潛力。然而已知對於噌啉鹽類之合成技術，效率較低且費用較高，有改善的空間。The application of cinnoline salts in organic photoelectric materials has attracted increasing attention, especially those with high molecular weight and good solubility in organic solvents, which have high potential. However, it is known that the synthesis technology of cinnoline salts has low efficiency and high cost, and there is room for improvement.

本發明之主要目的在於提供一種11-芳香基噌啉[2,3-f]菲啶鹽化合物，具有較佳的產率及較經濟的生產成本。The main purpose of the present invention is to provide a 11-arylcinnolin[2,3-f]phenanthridine salt compound, which has better yield and lower production cost.

本發明之另一目的在於提供一種11-芳香基噌啉[2,3-f]菲啶鹽化合物製造方法，具有較佳的產率及較經濟的生產成本。Another object of the present invention is to provide a method for producing 11-arylcinnolin[2,3-f]phenanthridine salt compound, which has better yield and lower production cost.

本發明之11-芳香基噌啉[2,3-f]菲啶鹽化合物，具有以下式（1）的結構：

Figure 02_image004
式（1）； 其中，R1 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R2 選自氫（H）、氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R選自由酯（ester，CO2 R'）、醯胺（amide，CONR'2 ）、酮（keto，COR'）、芳（aryl，Ar）、腈（nitrile，CN）、硝(nitro，NO2 )、三氟甲基(CF3 )、膦酸酯(phosphonate，P(=O)OR'2 )、膦氧化物(phosphine oxide，P(=O)R'2 )、磺醯基(sulfonyl，SOR')、及硫氧化物(sulfur oxide，SO2 R')構成的群組，R'選自由烷基(alkyl)以及芳基(aryl)構成的群組。The 11-arylcinnolin[2,3-f]phenanthridine salt compound of the present invention has the structure of the following formula (1):
Figure 02_image004
 Formula (1); Wherein, R 1 is selected from hydrogen (H), deuterium (D), methyl (Me), isopropyl ( iPr ), phenyl (Ph), oxymethyl (OMe), oxytri Fluoromethyl (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), nitrogen dimethyl (NMe 2 ), cyano (CN); R 2 is selected from hydrogen (H), deuterium (D) , Methyl (Me), Isopropyl ( i Pr), Phenyl (Ph), Oxymethyl (OMe), Oxytrifluoromethyl (OCF 3 ), Trifluoromethyl (CF 3 ), Fluorine (F ), nitrogen dimethyl (NMe 2 ), cyano (CN); R is selected from ester (ester, CO 2 R'), amide (amide, CONR' 2 ), ketone (keto, COR'), aromatic ( aryl, Ar), nitrile (nitrole, CN), nitrate (nitro, NO 2 ), trifluoromethyl (CF 3 ), phosphonate (phosphonate, P(=O)OR' 2 ), phosphine oxide (phosphine oxide, P(=O)R' 2 ), sulfonyl (sulfonyl, SOR'), and sulfur oxide (sulfur oxide, SO 2 R'), R' is selected from alkyl (alkyl) and Aryl (aryl) group.

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（A）的結構：

Figure 02_image006
式（A）； 其中，R選自由甲氧基羰基（methoxycarbonyl，CO2 Me）、丁氧基羰基（Butoxycarbonyl，CO2 Bu）、乙氧羰基（Ethoxycarbonyl，CO2 Et）、（苄氧基）羰基（(Benzyloxy)carbonyl，CO2 Bn）、（環己氧基）羰基（(Cyclohexyloxy)carbonyl，CO2 cyhex）、（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl）、苯氧基羰基（Phenoxycarbonyl，CO2 Ph）、二甲氨基甲醯基（Dimethylcarbamoyl，CONMe2 ）構成的群組。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the structure of the following formula (A):
Figure 02_image006
 Formula (A); wherein, R is selected from methoxycarbonyl (methoxycarbonyl, CO 2 Me), butoxycarbonyl (Butoxycarbonyl, CO 2 Bu), ethoxycarbonyl (Ethoxycarbonyl, CO 2 Et), (benzyloxy) Carbonyl ((Benzyloxy)carbonyl, CO 2 Bn), (cyclohexyloxy)carbonyl ((Cyclohexyloxy)carbonyl, CO 2 cyhex), ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2- yl)methoxy)carbonyl, CO 2 furfuryl), phenoxycarbonyl (CO 2 Ph), dimethylcarbamoyl (Dimethylcarbamoyl, CONMe 2 ).

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（A）的結構：

Figure 02_image008
式（A）； 其中，R選自由乙醯基（Acetyl，COMe）及苯基（phenyl，Ph）構成的群組。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the structure of the following formula (A):
Figure 02_image008
 Formula (A); wherein, R is selected from the group consisting of acetyl (Acetyl, COMe) and phenyl (phenyl, Ph).

在本發明的實施例中，如請求項1所述之11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（B）的結構：

Figure 02_image010
式（B）； 其中，R選自由（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl）及二甲氨基甲醯基（Dimethylcarbamoyl，CONMe2 ）構成的群組。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound as described in Claim 1 has the following structure of formula (B):
Figure 02_image010
 Formula (B); wherein, R is selected from ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2-yl)methoxy)carbonyl, CO 2 furfuryl) and dimethylcarbamoyl (Dimethylcarbamoyl, CONMe 2 ) group.

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含15-（二甲氨基甲醯基）-7,14-二甲基-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate），具有以下式（C）的結構：

Figure 02_image012
式（C）； 其中，R包含（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl）。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound comprises 15-(dimethylaminoformyl)-7,14-dimethyl-11-phenylcinnolin Phenyl[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate), with The structure of the following formula (C):
Figure 02_image012
 Formula (C); wherein, R contains ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2-yl)methoxy)carbonyl, CO 2 furfuryl).

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含15-（丁氧基羰基）-3-甲基-11-（間甲苯基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Butoxycarbonyl)-3-methyl-11-(m -tolyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate）， 具有以下式（D）的結構：

Figure 02_image014
式（D）； 其中，R包含丁氧基羰基（Butoxycarbonyl，CO2 Bu），R2 包含甲基（Me）。[ 2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Butoxycarbonyl)-3-methyl-11-( m -tolyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate) , has the following structure (D):
Figure 02_image014
 Formula (D); wherein, R contains butoxycarbonyl (Butoxycarbonyl, CO 2 Bu), and R 2 contains methyl (Me).

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含3-氟-11-（3-氟苯基）-15-（（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate）， 具有以下式（E）的結構：

Figure 02_image014
式（E）； 其中，R包含（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl），R2 包含氟。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound contains 3-fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2- base)methoxy)carbonyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl )methoxy)carbonyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate) , which has the structure of the following formula (E):
Figure 02_image014
 Formula (E); wherein, R contains ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2-yl)methoxy)carbonyl, CO 2 furfuryl), and R 2 contains fluorine.

在本發明的實施例中，如請求項1所述之11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含15-（丁氧基羰基）-4-氯-11-（2-氯苯基）噌啉[2,3-氟]菲啶9鎓[15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolino[2,3-f]phenanthridin-9-ium tetrafluoroborate]， 具有以下式（F）的結構：

Figure 02_image016
式（F）。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound as described in Claim 1 comprises 15-(butoxycarbonyl)-4-chloro-11-( 2-Chlorophenyl)cinnolino[2,3-fluoro]phenanthridin-9-ium[15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolino[2,3-f]phenanthridin-9-ium tetrafluoroborate] , which has the structure of formula (F):
Figure 02_image016
 Formula (F).

在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含14-（（（四氫呋喃-2-基）甲氧基）羰基）-10-（噻吩-2-基）噻吩并[3'，2'：3,4]喹啉并[1,2-b]噌啉-8-鎓 四氟硼酸鹽（14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno[3',2':3,4]quinolino[1,2-b ]cinnolin-8-ium tetrafluoroborate），具有以下式（G）的結構：

Figure 02_image018
式（G）。In an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound contains 14-(((tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophene- 2-yl)thieno[3',2':3,4]quinolino[1,2-b]cinnolin-8-ium tetrafluoroborate (14-(((Tetrahydrofuran-2-yl)methoxy )carbonyl)-10-(thiophen-2-yl)thieno[3',2':3,4]quinolino[1,2- b ]cinnolin-8-ium tetrafluoroborate), having the structure of formula (G):
Figure 02_image018
 Formula (G).

本發明的11-芳香基噌啉[2,3-f]菲啶鹽化合物的製造方法，藉由以下反應式製成11-芳香基噌啉[2,3-f]菲啶鹽化合物，

Figure 02_image020
其中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（1）的結構：
Figure 02_image022
 式（1）； R1 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R2 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R選自由酯（ester，CO2 R'）、醯胺（amide，CONR'2 ）、酮（keto，COR'）、芳（aryl，Ar）、腈（nitrile，CN）、硝(nitro，NO2 )、三氟甲基(CF3 ), 膦酸酯(phosphonate，P(=O)OR'2 )、膦氧化物(phosphine oxide，P(=O)R'2 )、磺醯基(sulfonyl，SOR')、及硫氧化物(sulfur oxide，SO2 R')構成的群組，R'選自由烷基(alkyl)以及芳基(aryl)構成的群組。The manufacture method of the 11-aryl cinnoline [2,3-f] phenanthridine salt compound of the present invention is to prepare the 11-aryl cinnoline [2,3-f] phenanthridine salt compound by the following reaction formula,
Figure 02_image020
 Among them, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the structure of the following formula (1):
Figure 02_image022
 Formula (1); R 1 is selected from hydrogen (H), deuterium (D), methyl (Me), isopropyl ( iPr ), phenyl (Ph), oxygen methyl (OMe), oxygen trifluoromethane (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), nitrogen dimethyl (NMe 2 ), cyano (CN); R 2 is selected from hydrogen (H), deuterium (D), methyl radical (Me), isopropyl ( i Pr), phenyl (Ph), oxymethyl (OMe), oxytrifluoromethyl (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), Nitrogen dimethyl (NMe 2 ), cyano (CN); R is selected from ester (ester, CO 2 R'), amide (amide, CONR' 2 ), ketone (keto, COR'), aromatic (aryl, Ar), nitrile (CN), nitrate (nitro, NO 2 ), trifluoromethyl (CF 3 ), phosphonate (phosphonate, P(=O)OR' 2 ), phosphine oxide (phosphine oxide, A group consisting of P(=O)R' 2 ), sulfonyl (sulfonyl, SOR'), and sulfur oxide (sulfur oxide, SO 2 R'), R' is selected from alkyl and aryl (aryl) group.

Figure 02_image024
在本發明的實施例中，2-偶氮二芳基（2-diazobiaryls）係藉由以下反應式製成，
Figure 02_image026
其中，2-偶氮二芳基具有以下式（2）的結構： 式（2）。
Figure 02_image024
In an embodiment of the present invention, 2-diazobiaryls are prepared by the following reaction formula,
Figure 02_image026
Wherein, 2-azobisaryl has the structure of the following formula (2): Formula (2).

本發明之11-芳香基噌啉[2,3-f]菲啶鹽化合物，具有以下式（1）的結構：

Figure 02_image028
式（1）； 其中，R1 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R2 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R選自由酯（ester，CO2 R'）、醯胺（amide，CONR'2 ）、酮（keto，COR'）、芳（aryl，Ar）、腈（nitrile，CN）、硝(nitro，NO2 )、三氟甲基(CF3 )、膦酸酯(phosphonate，P(=O)OR'2 )、膦氧化物(phosphine oxide，P(=O)R'2 )、磺醯基(sulfonyl，SOR')、及硫氧化物(sulfur oxide，SO2 R')構成的群組，R'選自由烷基(alkyl)以及芳基(aryl)構成的群組。The 11-arylcinnolin[2,3-f]phenanthridine salt compound of the present invention has the structure of the following formula (1):
Figure 02_image028
 Formula (1); Wherein, R 1 is selected from hydrogen (H), deuterium (D), methyl (Me), isopropyl ( iPr ), phenyl (Ph), oxymethyl (OMe), oxytri Fluoromethyl (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), nitrogen dimethyl (NMe 2 ), cyano (CN); R 2 is selected from hydrogen (H), deuterium (D) , Methyl (Me), Isopropyl ( i Pr), Phenyl (Ph), Oxymethyl (OMe), Oxytrifluoromethyl (OCF 3 ), Trifluoromethyl (CF 3 ), Fluorine (F ), nitrogen dimethyl (NMe 2 ), cyano (CN); R is selected from ester (ester, CO 2 R'), amide (amide, CONR' 2 ), ketone (keto, COR'), aromatic ( aryl, Ar), nitrile (nitrole, CN), nitrate (nitro, NO 2 ), trifluoromethyl (CF 3 ), phosphonate (phosphonate, P(=O)OR' 2 ), phosphine oxide (phosphine oxide, P(=O)R' 2 ), sulfonyl (sulfonyl, SOR'), and sulfur oxide (sulfur oxide, SO 2 R'), R' is selected from alkyl (alkyl) and Aryl (aryl) group.

在一實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物藉由以下反應式製成，

Figure 02_image020
其中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（1）的結構：
Figure 02_image030
 式（1）； R1 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R2 選自氫（H）、 氘（D）、甲基（Me）、異丙基（i Pr）、苯基（Ph）、氧甲基（OMe）、氧三氟甲基（OCF3 ）、三氟甲基（CF3 ）、氟（F）、氮二甲基（NMe2 ）、氰基（CN）； R選自由酯（ester，CO2 R'）、醯胺（amide，CONR'2 ）、酮（keto，COR'）、芳（aryl，Ar）、腈（nitrile，CN）、硝(nitro，NO2 )、三氟甲基(CF3 )、膦酸酯(phosphonate，P(=O)OR'2 )、膦氧化物(phosphine oxide，P(=O)R'2 )、磺醯基(sulfonyl，SOR')、及硫氧化物(sulfur oxide，SO2 R')構成的群組，R'選自由烷基(alkyl)以及芳基(aryl)構成的群組。In one embodiment, the 11-aryl cinnolin [2,3-f] phenanthridine salt compound is prepared by the following reaction formula,
Figure 02_image020
 Among them, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the structure of the following formula (1):
Figure 02_image030
 Formula (1); R 1 is selected from hydrogen (H), deuterium (D), methyl (Me), isopropyl ( iPr ), phenyl (Ph), oxygen methyl (OMe), oxygen trifluoromethane (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), nitrogen dimethyl (NMe 2 ), cyano (CN); R 2 is selected from hydrogen (H), deuterium (D), methyl radical (Me), isopropyl ( i Pr), phenyl (Ph), oxymethyl (OMe), oxytrifluoromethyl (OCF 3 ), trifluoromethyl (CF 3 ), fluorine (F), Nitrogen dimethyl (NMe 2 ), cyano (CN); R is selected from ester (ester, CO 2 R'), amide (amide, CONR' 2 ), ketone (keto, COR'), aromatic (aryl, Ar), nitrile (CN), nitrate (nitro, NO 2 ), trifluoromethyl (CF 3 ), phosphonate (phosphonate, P(=O)OR' 2 ), phosphine oxide (phosphine oxide, A group consisting of P(=O)R' 2 ), sulfonyl (sulfonyl, SOR'), and sulfur oxide (sulfur oxide, SO 2 R'), R' is selected from alkyl and aryl (aryl) group.

更具體而言，在一實施例中，如下列反應式，

Figure 02_image032
係在一包含2-偶氮二芳基（2-azo-biaryls）（上式中標記2a，0.1 mmol）的密封試管中加入Pd(OAc)2 （0.01 mmol，2.2 mg）、Cu(OAc)2 （0.3 mmol，54.3 mg）以及CuCl2 （0.3 mmol，40.4 mg）。而後，三氟乙醇（triflouroethanol，TFE，2.0 mL）及丙烯酸丁酯（butyl acrylate，上式中標記3b，0.2 mmol）依序先後以注射器在空氣中被加入混合物。混合物被加熱到100至120℃達12至16小時。反應結果混合物被冷卻到室溫並以CH2 Cl2 （10 mL）稀釋，然後此溶液被真空濃縮且殘餘物以矽膠管柱層析純化（Pet ether; EtOAc/MeOH (~5%)）作為複合中間體。然後，此複合中間體在二氯甲烷溶劑中以AgBF4 （2.5 eqiuv）處理，在室溫中攪拌2至5分鐘，再通過矽藻土過濾並真空濃縮濾出物作為所需產率的15-（丁氧基羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽鹽類（上式中標記4ab）。More specifically, in one embodiment, as the following reaction formula,
Figure 02_image032
 Add Pd(OAc) 2 (0.01 mmol, 2.2 mg), Cu(OAc) 2 (0.3 mmol, 54.3 mg) and CuCl 2 (0.3 mmol, 40.4 mg). Then, trifluoroethanol (TFE, 2.0 mL) and butyl acrylate (butyl acrylate, marked 3b in the above formula, 0.2 mmol) were sequentially added to the mixture by syringe in air. The mixture is heated to 100 to 120°C for 12 to 16 hours. The resulting reaction mixture was cooled to room temperature and diluted with CH 2 Cl 2 (10 mL), then the solution was concentrated in vacuo and the residue was purified by silica gel column chromatography (Pet ether; EtOAc/MeOH (~5%)) as Composite intermediates. This complex intermediate was then treated with AgBF 4 (2.5 eqiuv) in dichloromethane solvent, stirred at room temperature for 2 to 5 min, filtered through celite and the filtrate was concentrated in vacuo as 15% in the desired yield. -(Butoxycarbonyl)-11-phenylcinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate salts (labeled 4ab in the above formula).

其中，前述標記標記4ab的鹽類，其性質量測結果為：Red solid; m.p. 204-209 °C; 1 H NMR (700 MHz, CDCl3 ): δ 8.87 (d,J = 8.4 Hz, 1 H), 8.78 (d,J = 8.4 Hz, 1 H), 8.75 (d,J = 7.7 Hz, 1 H), 8.60 (d,J = 8.4 Hz, 1 H), 8.35-8.29 (m, 3 H), 8.12 (t,J = 7.7 Hz, 1 H), 8.00 (t,J = 7.7 Hz, 1 H), 7.99-7.85 (m, 4 H), 7.67-7.64 (m, 3 H), 4.67 (t,J = 11.2 Hz, 2 H), 1.78-1.75 (m, 2 H), 1.36-1.32 (m, 2 H), 0.91 (t,J = 7.7 Hz, 3 H); 13 C NMR (175 MHz, CDCl3 ): δ 164.7, 145.8, 142.4, 138.8, 137.8, 136.7, 135.6, 135.3, 134.9, 134.7, 132.8, 132.0, 131.3, 130.1, 129.8, 129.6, 128.8, 128.4, 126.7, 126.0, 124.0, 123.8, 123.2, 121.9, 121.5, 68.7, 29.9, 18.9, 13.5; 11 B NMR (191 MHz, CDCl3 ): δ -2.89; 19 F NMR (563 MHz, CDCl3 ): δ -153.52, -153.57 and secondary isotopic shift (10 B,11 B) of 0.05 ppm;HRMS (ESI+ ) calcd  for C31 H25 N2 O2 + 457.1911, found 457.1910; IR (KBr): 3085, 1675, 1581, 1056 (νB-F ), 775 and 502 cm-1 。Among them, the above-mentioned salts marked with 4ab have properties and mass measurements: Red solid; mp 204-209 °C; 1 H NMR (700 MHz, CDCl 3 ): δ 8.87 (d, J = 8.4 Hz, 1 H ), 8.78 (d, J = 8.4 Hz, 1 H), 8.75 (d, J = 7.7 Hz, 1 H), 8.60 (d, J = 8.4 Hz, 1 H), 8.35-8.29 (m, 3 H) , 8.12 (t, J = 7.7 Hz, 1 H), 8.00 (t, J = 7.7 Hz, 1 H), 7.99-7.85 (m, 4 H), 7.67-7.64 (m, 3 H), 4.67 (t , J = 11.2 Hz, 2 H), 1.78-1.75 (m, 2 H), 1.36-1.32 (m, 2 H), 0.91 (t, J = 7.7 Hz, 3 H); 13 C NMR (175 MHz, CDCl 3 ): δ 164.7, 145.8, 142.4, 138.8, 137.8, 136.7, 135.6, 135.3, 134.9, 134.7, 132.8, 132.0, 131.3, 130.1, 129.8, 129.6, 128.8, 128.4, 126.7, 126.0, 124.0, 123.8, 123.2 , 121.9, 121.5, 68.7, 29.9, 18.9, 13.5; 11 B NMR (191 MHz, CDCl 3 ): δ -2.89; 19 F NMR (563 MHz, CDCl 3 ): δ -153.52, -153.57 and secondary isotopic shift ( 10 B, 11 B) of 0.05 ppm; HRMS (ESI + ) calcd for C 31 H 25 N 2 O 2 + 457.1911, found 457.1910; IR (KBr): 3085, 1675, 1581, 1056 (ν BF ), 775 and 502 cm -1 .

在本發明的實施例中，2-偶氮二芳基（2-diazobiaryls）係藉由以下反應式製成，

Figure 02_image034
其中，2-偶氮二芳基具有以下式（2）的結構：
Figure 02_image036
 式（2）。In an embodiment of the present invention, 2-diazobiaryls are prepared by the following reaction formula,
Figure 02_image034
 Among them, 2-azobisaryl has the structure of the following formula (2):
Figure 02_image036
 Formula (2).

更具體而言，取代的2-胺二芳基（2-amino-biaryl）（上式中標記為1a，2.00 mmol）被置於圓底燒瓶中且溶於甲苯（15 mL），接著在0℃的氮氣環境中分批添加間氯過氧化苯甲酸（meta -chloroperoxybenzoic acid，516 mg，3.00 mmol）。反應混合物在室溫中攪拌12至18小時。而後粗產物以快速管柱層析（flash column chromatography）純化（(2% EtOAc in petrolium ether）作為70％產率的橙色固體的所需產物（上式中標記2a）。More specifically, a substituted 2-amino-biaryl (labeled 1a in the above formula, 2.00 mmol) was placed in a round bottom flask and dissolved in toluene (15 mL), followed by 0 m-chloroperoxybenzoic acid ( meta -chloroperoxybenzoic acid, 516 mg, 3.00 mmol) was added in batches under nitrogen atmosphere at ℃. The reaction mixture was stirred at room temperature for 12 to 18 hours. The crude product was then purified by flash column chromatography (2% EtOAc in petrolium ether) as the desired product (labeled 2a in the above formula) as an orange solid in 70% yield.

在不同實施例中，如下列反應式，

Figure 02_image038
在一包含2-azo-biaryls（上式中標記2a，0.1 mmol）的密封試管中加入Pd(OAc)2 （0.01 mmol，2.2 mg）、Cu(OAc)2 （0.3 mmol，54.3 mg）以及PivOH（0.3 mmol，40.4 mg）。而後，三氟乙醇（triflouroethanol，TFE，2.0 mL）及丙烯酸丁酯（butyl acrylate，上式中標記3b，0.2 mmol）依序先後以注射器在空氣中被加入混合物。混合物被加熱到100至120℃達12至16小時。反應結果混合物被冷卻到室溫並以CH2 Cl2 （10 mL）稀釋，然後此溶液被真空濃縮且殘餘物以矽膠管柱層析純化（Pet ether; EtOAc/MeOH (~5%)）作為複合中間體。然後，此複合中間體在二氯甲烷溶劑中以AgBF4 （2.5 eqiuv）處理，在室溫中攪拌2至5分鐘，再通過矽藻土過濾並真空濃縮濾出物作為所需產率的15-（丁氧基羰基）-15-羥基-11-苯基-15H-噌啉[2,3-f ]菲啶-9-鎓-10-鹽鹽類（上式中標記5ab）。其中，此標記為5ab的鹽類較佳儲存於5℃的甲醇中。In different embodiments, as the following reaction formula,
Figure 02_image038
 Add Pd(OAc) 2 (0.01 mmol, 2.2 mg), Cu(OAc) 2 (0.3 mmol, 54.3 mg) and PivOH to a sealed tube containing 2-azo-biaryls (labeled 2a in the above formula, 0.1 mmol) (0.3 mmol, 40.4 mg). Then, trifluoroethanol (TFE, 2.0 mL) and butyl acrylate (butyl acrylate, marked 3b in the above formula, 0.2 mmol) were sequentially added to the mixture by syringe in air. The mixture is heated to 100 to 120°C for 12 to 16 hours. The resulting reaction mixture was cooled to room temperature and diluted with CH 2 Cl 2 (10 mL), then the solution was concentrated in vacuo and the residue was purified by silica gel column chromatography (Pet ether; EtOAc/MeOH (~5%)) as Composite intermediates. This complex intermediate was then treated with AgBF 4 (2.5 eqiuv) in dichloromethane solvent, stirred at room temperature for 2 to 5 min, filtered through celite and the filtrate was concentrated in vacuo as 15% in the desired yield. -(Butoxycarbonyl)-15-hydroxy-11-phenyl-15H-cinnolin[2,3- f ]phenanthridin-9-ium-10-salts (labeled 5ab in the above formula). Among them, the salt labeled 5ab is preferably stored in methanol at 5°C.

換言之，與以上列反應式類似地，以2-azo-biaryls及丙烯酸丁酯為反應物，使用Pd(OAc)2 做為觸媒，可生成11-芳香基噌啉[2,3-f]菲啶鹽化合物。進一步而言，係由鈀催化的2-偶氮二芳基和烯烴的高度區域選擇性合成11-苯基亞氨基[2,3-f]菲啶-9-鹽。該反應通過烯烴的雙氧化C-H偶聯進行，得到中等收率的多環噌啉菲啶鹽。反應機理包括通過烯烴對2-偶氮二芳基進行鄰C-H烯化、分子內氮雜-麥可加成、β-氫化物消去、親電子鈀化，然後進行分子內C-H活化和還原消去。另一方面，生成11-芳香基噌啉[2,3-f]菲啶鹽化合物具有高分子量，在各種有機溶劑中具有良好的溶解性，例如他們能溶於甲苯、二氯甲烷、氯仿、二氯苯、1,4-二氧陸圜及四氫呋喃等溶劑，每毫升至少能溶解20毫克以上的鹽化合物。並且，該鹽化合物在用於溶液製程橙紅色OLED材料具有高潛力。過去橘紅色發光材料均仰賴有過渡金屬的發光體，該含金屬的發光體性質一般呈現較低的內部量子產率及較寬的光帶。由於不含金屬的發光體於有機溶劑有較好的溶解度及量子產率，近來的發展逐漸朝向不含金屬的有機材料設計與合成。該類的有機材料一般有推拉電子的官能基，導致電子轉移，呈現較窄寬帶的橘紅色有機發光二極體。因此，目前所提出的11-芳香基噌啉[2,3-f]菲啶鹽化合物將具有高度潛力作為溶液製程的橙紅色OLED材料。In other words, similar to the above reaction formula, 11-arylcinnoline[2,3-f] can be produced by using 2-azo-biaryls and butyl acrylate as reactants and using Pd(OAc) 2 as a catalyst Phenanthridine salt compound. Further, a palladium-catalyzed highly regioselective synthesis of 11-phenylimino[2,3-f]phenanthridine-9-salts from 2-azobisaryls and alkenes. The reaction proceeds via a double-oxidative CH coupling of alkenes to afford polycyclic cinnoline phenanthridine salts in moderate yields. The reaction mechanism involves ortho-CH olefination of 2-azobisaryl groups via alkenes, intramolecular aza-Micco addition, β-hydride elimination, electrophilic palladium, followed by intramolecular CH activation and reductive elimination. On the other hand, generate 11-aryl cinnoline [2,3-f] phenanthridine salt compounds with high molecular weight, have good solubility in various organic solvents, for example they can be dissolved in toluene, methylene chloride, chloroform, Solvents such as dichlorobenzene, 1,4-dioxane, and tetrahydrofuran can dissolve at least 20 mg of salt compounds per ml. Moreover, the salt compound has high potential for solution-processed orange-red OLED materials. In the past, orange-red luminescent materials relied on luminophores containing transition metals, and the properties of such metal-containing luminophores generally exhibited low internal quantum yields and wide optical bands. Due to the better solubility and quantum yield of metal-free luminophores in organic solvents, recent developments are gradually directed towards the design and synthesis of metal-free organic materials. This type of organic material generally has functional groups that push and pull electrons, resulting in electron transfer, and presents an orange-red organic light-emitting diode with a narrow bandwidth. Therefore, the presently proposed 11-arylcinnolin[2,3-f]phenanthridinium compounds will have high potential as solution-processed orange-red OLED materials.

更具體而言，在本發明的實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（A）的結構：

Figure 02_image006
式（A）； 其中，R選自由甲氧基羰基（methoxycarbonyl，CO2 Me）、丁氧基羰基（Butoxycarbonyl，CO2 Bu）、乙氧羰基（Ethoxycarbonyl，CO2 Et）、（苄氧基）羰基（(Benzyloxy)carbonyl，CO2 Bn）、（環己氧基）羰基（(Cyclohexyloxy)carbonyl，CO2 cyhex）、（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl）、苯氧基羰基（Phenoxycarbonyl，CO2 Ph）、二甲氨基甲醯基（Dimethylcarbamoyl，CONMe2 ）構成的群組。進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表1。 表1 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4aa 15-（甲氧基羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Methoxycarbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ab 15-（丁氧基羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Butoxycarbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ac 15-（乙氧羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Ethoxycarbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ad 15-（（苄氧基）羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-((Benzyloxy)carbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ae 15-（（環己氧基）羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-((Cyclohexyloxy)carbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4af 11-苯基-15-（（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]-菲啶-9-鎓四氟硼酸鹽（11-Phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ag 15-（苯氧基羰基）-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Phenoxycarbonyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4ah 15-（二甲氨基甲醯基）-11-苯基噌啉[2,3-f]菲啶-9-鎓四氟硼酸鹽（15-(Dimethylcarbamoyl)-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） More specifically, in an embodiment of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the structure of the following formula (A):
Figure 02_image006
 Formula (A); wherein, R is selected from methoxycarbonyl (methoxycarbonyl, CO 2 Me), butoxycarbonyl (Butoxycarbonyl, CO 2 Bu), ethoxycarbonyl (Ethoxycarbonyl, CO 2 Et), (benzyloxy) Carbonyl ((Benzyloxy)carbonyl, CO 2 Bn), (cyclohexyloxy)carbonyl ((Cyclohexyloxy)carbonyl, CO 2 cyhex), ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2- yl)methoxy)carbonyl, CO 2 furfuryl), phenoxycarbonyl (CO 2 Ph), dimethylcarbamoyl (Dimethylcarbamoyl, CONMe 2 ). Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 1 below. Table 1 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4aa 15-(Methoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Methoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin -9-ium tetrafluoroborate) 4ab 15-(Butoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Butoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin -9-ium tetrafluoroborate) 4ac 15-(Ethoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Ethoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin- 9-ium tetrafluoroborate) 4ad 15-((Benzyloxy)carbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-((Benzyloxy)carbonyl)-11-phenylcinnolino[2, 3- f ]phenanthridin-9-ium tetrafluoroborate) 4ae 15-((Cyclohexyloxy)carbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-((Cyclohexyloxy)carbonyl)-11-phenylcinnolino[2 ,3- f ]phenanthridin-9-ium tetrafluoroborate) 4af 11-Phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnoline[2,3- f ]-phenanthridine-9-ium tetrafluoroborate (11-Phenyl-15-( ((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate) 4ag 15-(Phenoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Phenoxycarbonyl)-11-phenylcinnolino[2,3- f ]phenanthridin -9-ium tetrafluoroborate) 4ah 15-(Dimethylcarbamoyl)-11-phenylcinnolino[2,3-f]phenanthridin-9-ium tetrafluoroborate (15-(Dimethylcarbamoyl)-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（A）的結構：

Figure 02_image006
式（A）； 其中，R選自由乙醯基（Acetyl，COMe）及苯基（phenyl，Ph）構成的群組。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表2。 表2 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4ai 15-乙醯基-11-苯基噌啉[2,3-f]菲啶-9-鎓四氟硼酸鹽（15-Acetyl-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4aj 11,15-二苯基噌啉[2,3-f]菲啶-9-鎓四氟硼酸鹽（11,15-Diphenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） In different embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound has the following structure of formula (A):
Figure 02_image006
 Formula (A); wherein, R is selected from the group consisting of acetyl (Acetyl, COMe) and phenyl (phenyl, Ph). Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 2 below. Table 2 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4ai 15-Acetyl-11-phenylcinnolino[2,3-f]phenanthridin-9-ium tetrafluoroborate (15-Acetyl-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate ) 4aj 11,15-Diphenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate

在本發明的不同實施例中，如請求項1所述之11-芳香基噌啉[2,3-f]菲啶鹽化合物具有以下式（B）的結構：

Figure 02_image041
式（B）； 其中，R選自由（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl）及二甲氨基甲醯基（Dimethylcarbamoyl，CONMe2 ）構成的群組。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表3。 表3 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4bf 7,14-二甲基-11-苯基-15-（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（7,14-Dimethyl-11-phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） 4bh 15-（二甲氨基甲醯基）-7,14-二甲基-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） In different embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound as described in Claim 1 has the structure of the following formula (B):
Figure 02_image041
 Formula (B); wherein, R is selected from ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2-yl)methoxy)carbonyl, CO 2 furfuryl) and dimethylcarbamoyl (Dimethylcarbamoyl, CONMe 2 ) group. Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 3 below. table 3 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4bf 7,14-Dimethyl-11-phenyl-15-((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (7 ,14-Dimethyl-11-phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate) 4bh 15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Dimethylcarbamoyl)-7 ,14-dimethyl-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含15-（二甲氨基甲醯基）-7,14-二甲基-11-苯基噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate），具有以下式（C）的結構：

Figure 02_image043
式（C）。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表4。 表4 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4cf 6,13-二甲基-11-苯基-15-（（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（6,13-Dimethyl-11-phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） In various embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound comprises 15-(dimethylaminoformyl)-7,14-dimethyl-11-phenyl Cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Dimethylcarbamoyl)-7,14-dimethyl-11-phenylcinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate), has the following structure (C):
Figure 02_image043
 Formula (C). Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 4 below. Table 4 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4cf 6,13-Dimethyl-11-phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate ( 6,13-Dimethyl-11-phenyl-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含15-（丁氧基羰基）-3-甲基-11-（間甲苯基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Butoxycarbonyl)-3-methyl-11-(m -tolyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate）， 具有以下式（D）的結構：

Figure 02_image045
式（D）； 其中，R包含丁氧基羰基（Butoxycarbonyl，CO2 Bu），R2 包含甲基（Me）。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表5。 表5 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4db 15-（丁氧基羰基）-3-甲基-11-（間甲苯基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（15-(Butoxycarbonyl)-3-methyl-11-(m -tolyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） In various embodiments of the invention, the 11-arylcinnolin[2,3-f]phenanthrinium salt compound comprises 15-(butoxycarbonyl)-3-methyl-11-(m-tolyl)cinnoline [ 2,3- f ] phenanthridin-9- ium tetrafluoroborate , has the structure of the following formula (D):
Figure 02_image045
 Formula (D); wherein, R contains butoxycarbonyl (Butoxycarbonyl, CO 2 Bu), and R 2 contains methyl (Me). Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 5 below. table 5 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4db 15-(Butoxycarbonyl)-3-methyl-11-(m-tolyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (15-(Butoxycarbonyl)-3-methyl -11-( m -tolyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含3-氟-11-（3-氟苯基）-15-（（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽（3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate）， 具有以下式（E）的結構：

Figure 02_image014
式（E）； 其中，R包含（（四氫呋喃-2-基）甲氧基）羰基（((tetrahydrofuran-2-yl)methoxy)carbonyl，CO2 furfuryl），R2 包含氟。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表6。 表6 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4ef 3-氟-11-（3-氟苯基）-15-（（（四氫呋喃-2-基）甲氧基）羰基）噌啉[2,3-f ]菲啶-9-鎓四氟硼酸鹽 （3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl) cinnolino[2,3-f ]phenanthridin-9-ium tetrafluoroborate） In different embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound comprises 3-fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2 -yl)methoxy)carbonyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2- yl)methoxy)carbonyl)cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate) , which has the structure of the following formula (E):
Figure 02_image014
 Formula (E); wherein, R contains ((tetrahydrofuran-2-yl)methoxy)carbonyl (((tetrahydrofuran-2-yl)methoxy)carbonyl, CO 2 furfuryl), and R 2 contains fluorine. Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 6 below. Table 6 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4ef 3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl)cinnolin[2,3- f ]phenanthridin-9-ium tetrafluoroborate (3-Fluoro-11-(3-fluorophenyl)-15-(((tetrahydrofuran-2-yl)methoxy)carbonyl) cinnolino[2,3- f ]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，如請求項1所述之11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含15-（丁氧基羰基）-4-氯-11-（2-氯苯基）噌啉[2,3-氟]菲啶9鎓（15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolino[2,3-f]phenanthridin- 9-ium tetrafluoroborate）， 具有以下式（F）的結構：

Figure 02_image016
式（F）。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表7。 表7 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4fb 15-（丁氧基羰基）-4-氯-11-（2-氯苯基）噌啉[2,3-氟]菲啶9鎓（15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolino[2,3-f] phenanthridin-9-ium tetrafluoroborate） In different embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridine salt compound as described in claim 1, comprising 15-(butoxycarbonyl)-4-chloro-11- (2-Chlorophenyl)cinnolino[2,3-fluoro]phenanthridin-9-onium (15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolino[2,3-f]phenanthridin-9- ium tetrafluoroborate) , which has the structure of the following formula (F):
Figure 02_image016
 Formula (F). Further, the 11-arylcinnolin[2,3-f]phenanthridine salt compounds are included in Table 7 below. Table 7 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4fb 15-(butoxycarbonyl)-4-chloro-11-(2-chlorophenyl)cinnolin[2,3-fluoro]phenanthridine 9-ium (15-(butoxycarbonyl)-4-chloro-11-(2 -chlorophenyl)cinnolino[2,3-f]phenanthridin-9-ium tetrafluoroborate)

在本發明的不同實施例中，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含14-（（（四氫呋喃-2-基）甲氧基）羰基）-10-（噻吩-2-基）噻吩并[3'，2'：3,4]喹啉并[1,2-b]噌啉-8-鎓 四氟硼酸鹽（14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno[3',2':3,4]quinolino[1,2-b ]cinnolin-8-ium tetrafluoroborate），具有以下式（G）的結構：

Figure 02_image049
式（G）。 進一步而言，11-芳香基噌啉[2,3-f]菲啶鹽化合物包含如下表8。 表8 編號 11-芳香基噌啉[2,3-f]菲啶鹽化合物名稱 4gf 14-（（（四氫呋喃-2-基）甲氧基）羰基）-10-（噻吩-2-基）噻吩并[3'，2'：3,4]喹啉并[1,2-b]噌啉-8-鎓 四氟硼酸鹽（14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno [3',2':3,4]quinolino[1,2-b ]cinnolin-8-ium tetrafluoroborate） In various embodiments of the present invention, the 11-arylcinnolin[2,3-f]phenanthridinium salt compound comprises 14-(((tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophene- 2-yl)thieno[3',2':3,4]quinolino[1,2-b]cinnolin-8-ium tetrafluoroborate (14-(((Tetrahydrofuran-2-yl)methoxy )carbonyl)-10-(thiophen-2-yl)thieno[3',2':3,4]quinolino[1,2- b ]cinnolin-8-ium tetrafluoroborate), having the structure of formula (G):
Figure 02_image049
 Formula (G). Further, the 11-arylcinnolin[2,3-f]phenanthrinium salt compounds are included in Table 8 below. Table 8 serial number 11-Arylcinnoline[2,3-f]phenanthridine salt compound name 4gf 14-(((tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thien-2-yl)thieno[3',2':3,4]quinolino[1,2-b] Cinnolin-8-ium tetrafluoroborate (14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno [3',2':3,4]quinolino[ 1,2- b ]cinnolin-8-ium tetrafluoroborate)

針對上述標記/編號為2a、4ab、4ad、4ah、4ag、4bf的化合物進行吸收及螢光測試（1.0 ×10-5 M, 激發波長 360 nm，在二氯甲烷中），結果分別如圖1及圖2所示。由圖1及圖2可知化合物2a在275-400 nm有最大吸收波峰，化合物4ab、4ad、4ah、4ag在340 nm有最大吸收波峰，化合物4bf在380 nm有最大吸收波峰。若以最大吸收波峰之波長激發2a、4ab、4ad、4ah、4ag、4bf的化合物，發現化合物2a並沒有螢光出現;然而化合物4ab、4ad、4ah、4ag、4bf被激發後，會有螢光放光出現在波長500-750 nm之間，呈現橘紅色。Absorption and fluorescence tests (1.0 × 10 -5 M, excitation wavelength 360 nm, in dichloromethane) were carried out on the above-mentioned compounds labeled/numbered 2a, 4ab, 4ad, 4ah, 4ag, and 4bf, and the results are shown in Figure 1 And as shown in Figure 2. From Figure 1 and Figure 2, it can be seen that compound 2a has a maximum absorption peak at 275-400 nm, compounds 4ab, 4ad, 4ah, and 4ag have maximum absorption peaks at 340 nm, and compound 4bf has a maximum absorption peak at 380 nm. If compounds 2a, 4ab, 4ad, 4ah, 4ag, and 4bf are excited at the wavelength of the maximum absorption peak, it is found that compound 2a does not show fluorescence; however, compounds 4ab, 4ad, 4ah, 4ag, and 4bf will fluoresce after being excited. The light emission occurs at a wavelength of 500-750 nm and appears orange-red.

雖然前述的描述及圖式已揭示本發明之較佳實施例，必須瞭解到各種增添、許多修改和取代可能使用於本發明較佳實施例，而不會脫離如所附申請專利範圍所界定的本發明原理之精神及範圍。熟悉本發明所屬技術領域之一般技藝者將可體會，本發明可使用於許多形式、結構、佈置、比例、材料、元件和組件的修改。因此，本文於此所揭示的實施例應被視為用以說明本發明，而非用以限制本發明。本發明的範圍應由後附申請專利範圍所界定，並涵蓋其合法均等物，並不限於先前的描述。Although the foregoing description and drawings have disclosed preferred embodiments of the present invention, it must be understood that various additions, modifications and substitutions may be applied to the preferred embodiments of the present invention without departing from the scope of the appended application as defined The spirit and scope of the principles of the invention. Those of ordinary skill in the art to which the invention pertains will appreciate that the invention can be employed with many modifications in form, structure, arrangement, proportion, material, element and assembly. Therefore, the embodiments disclosed herein should be regarded as illustrating the present invention rather than limiting the present invention. The scope of the present invention should be defined by the claims of the appended claims and cover their legal equivalents, not limited by the foregoing description.

（無）(none)

圖1為光吸收測試結果。Figure 1 shows the light absorption test results.

圖2為螢光測試結果。Figure 2 shows the results of the fluorescence test.

（無）(none)

Figure 110135685-A0101-11-0002-1
Figure 110135685-A0101-11-0002-1

Claims (1)

一種11-芳香基噌啉[2,3-f]菲啶鹽化合物，包含14-（（（四氫呋喃-2-基）甲氧基）羰基）-10-（噻吩-2-基）噻吩并[3'，2'：3,4]喹啉并[1,2-b]噌啉-8-鎓 四氟硼酸鹽（14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno[3',2':3,4]quinolino[1,2-b ]cinnolin-8-ium tetrafluoroborate），具有以下式（G）的結構：
Figure 03_image051
式（G）； 其中， R選自由酯（ester，CO2 R'）、醯胺（amide，CONR'2 ）、酮（keto，COR'）、芳（aryl，Ar）、腈（nitrile，CN）、硝(nitro，NO2 )、三氟甲基(CF3 )、膦酸酯(phosphonate，P(=O)OR'2 )、膦氧化物(phosphine oxide，P(=O)R'2 )、磺醯基(sulfonyl，SOR')、及硫氧化物(sulfur oxide，SO2 R')構成的群組，R' 選自由環烷基、四氫呋喃-2-基甲氧基（furfuryl）、烷基(alkyl)以及芳基(aryl)構成的群組。A 11-arylcinnolin[2,3-f]phenanthridine salt compound containing 14-(((tetrahydrofuran-2-yl)methoxy)carbonyl)-10-(thiophen-2-yl)thieno[ 3', 2': 3,4] quinolino[1,2-b]cinnolin-8-ium tetrafluoroborate (14-(((Tetrahydrofuran-2-yl)methoxy)carbonyl)-10-( thiophen-2-yl) thieno[3',2':3,4]quinolino[1,2- b ]cinnolin-8-ium tetrafluoroborate), having the structure of formula (G):
Figure 03_image051
Formula (G); wherein, R is selected from ester (ester, CO 2 R'), amide (amide, CONR' 2 ), ketone (keto, COR'), aromatic (aryl, Ar), nitrile (nitrole, CN ), nitrate (nitro, NO 2 ), trifluoromethyl (CF 3 ), phosphonate (phosphonate, P(=O)OR' 2 ), phosphine oxide (phosphine oxide, P(=O)R' 2 ), a group consisting of sulfonyl (sulfonyl, SOR'), and sulfur oxide (sulfur oxide, SO 2 R'), R' is selected from the group consisting of cycloalkyl, tetrahydrofuran-2-ylmethoxy (furfuryl), A group consisting of alkyl (alkyl) and aryl (aryl).
TW110135685A 2019-08-30 2019-08-30 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof TWI785816B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW110135685A TWI785816B (en) 2019-08-30 2019-08-30 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW110135685A TWI785816B (en) 2019-08-30 2019-08-30 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof

Publications (2)

Publication Number Publication Date
TW202200578A TW202200578A (en) 2022-01-01
TWI785816B true TWI785816B (en) 2022-12-01

Family

ID=80787790

Family Applications (1)

Application Number Title Priority Date Filing Date
TW110135685A TWI785816B (en) 2019-08-30 2019-08-30 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof

Country Status (1)

Country Link
TW (1) TWI785816B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI404704B (en) * 2004-03-03 2013-08-11 Takeda Gmbh Novel hydroxy-6-heteroarylphenanthridines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI404704B (en) * 2004-03-03 2013-08-11 Takeda Gmbh Novel hydroxy-6-heteroarylphenanthridines

Also Published As

Publication number Publication date
TW202200578A (en) 2022-01-01

Similar Documents

Publication Publication Date Title
TWI753296B (en) 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof
CN109988117B (en) Preparation method of 3-methylquinoxaline-2 (1H) -ketone derivatives
JP6341923B2 (en) Strong fluorescent luminescent heterocyclic compound and method for producing the same
CN113861143B (en) Thermal-activation delayed fluorescence deep blue light material, preparation method thereof and organic electroluminescent device
JPH07101911A (en) New pyrene derivative and its production
CN111732516B (en) A kind ofNProcess for preparing (E) -aryl-substituted heterocyclic compounds
TWI785816B (en) 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof
KR101460071B1 (en) Prepartion method for trifluoromethyl substituted heterocycles via visible light photoredox catalysis
CN114349609B (en) Synthesis method of hexabenzocoronene dimer
CN113735799B (en) Synthesis method of dyclonine hydrochloride
JP5330066B2 (en) Method for producing triarylamine compound
CN111233839B (en) (E) 1-acyl-2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole and preparation method thereof
CN111995637B (en) Organic compound and organic electroluminescent device thereof
CN113845491A (en) Benzophenothiazine derivatives and process for their preparation
TWI773602B (en) Triarylcinnolin-2-ium salts and method of manufacturing the same
CN111559973B (en) Spiroalkene derivative and preparation method and application thereof
CN115925677B (en) Fluorescent material containing sulfolane-olefin structural unit and preparation method thereof
CN110283124B (en) Pyridoindene compound and preparation method and application thereof
Ghanbari et al. Column chromatography: A facile and inexpensive procedure to purify the red dopant DCJ applied for OLEDs
CN118580171A (en) Oxetane trichloroacetimidate and preparation method and application thereof
JPWO2007105622A1 (en) Method for producing heterocyclic compound
JP2001163839A (en) Aminophenol compound, method for producing the same and synthetic intermediate
CN115677775A (en) Preparation method of dibenzophospholane pentadiene compound with electroluminescence function
CN114230577A (en) Synthesis method of oxazolopyridine compound
CN118496233A (en) Method for synthesizing pyrimido [1,2-a ] benzimidazole by taking calcium carbide as acetylene source in one pot and application