TWI773602B - Triarylcinnolin-2-ium salts and method of manufacturing the same - Google Patents

Triarylcinnolin-2-ium salts and method of manufacturing the same Download PDF

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TWI773602B
TWI773602B TW110144487A TW110144487A TWI773602B TW I773602 B TWI773602 B TW I773602B TW 110144487 A TW110144487 A TW 110144487A TW 110144487 A TW110144487 A TW 110144487A TW I773602 B TWI773602 B TW I773602B
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ring
triarylcinnoline
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salt compound
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TW202321200A (en
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莊士卿
詹孟穎
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國立陽明交通大學
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Abstract

A triarylcinnolin-2-ium salts has a structure represented by formula (1), in which R 1is selected from a group consisting of aryl group, alkyl group, and ethoxycarbonyl group; R 2is aryl group; R 3is hydrogen or methyl group; and ring A is an aromatic ring.

Description

三芳基噌啉鹽化合物及其製造方法Triarylcinnoline salt compound and method for producing the same

本發明是有關於一種三芳基噌啉鹽化合物及其製造方法。The present invention relates to a triarylcinnoline salt compound and a preparation method thereof.

噌啉鹽類可應用於有機發光二極體(OLEDs)、有機場效應電晶體(OFETs)材料、DNA嵌入劑(DNA intercalators)及生物追踪器(bio-trackers)等。然而，現有的製造方法效率較低且費用較高。因此，需要一種更有效且便宜的方法。Cinnoline salts can be used in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) materials, DNA intercalators, and bio-trackers. However, existing manufacturing methods are inefficient and expensive. Therefore, a more efficient and inexpensive method is needed.

根據本發明之各種實施方式，提供一種三芳基噌啉鹽化合物，具有以下式(1)的結構：

Figure 02_image001
式(1)； 其中R 1選自由芳基、烷基、及乙氧羰基所組成的群組；R 2為芳基；R 3為氫或甲基；以及環A為芳香環。 According to various embodiments of the present invention, there is provided a triarylcinnoline salt compound having the structure of the following formula (1):
Figure 02_image001
Formula (1); wherein R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl; R 2 is aryl; R 3 is hydrogen or methyl; and Ring A is an aromatic ring.

根據本發明之某些實施方式，三芳基噌啉鹽化合物具有以下式(2)的結構：

Figure 02_image006
式(2)； 其中R 1選自由苯基、乙基、丁基、及乙氧羰基所組成的群組。 According to certain embodiments of the present invention, the triarylcinnoline salt compound has the structure of the following formula (2):
Figure 02_image006
Formula (2); wherein R 1 is selected from the group consisting of phenyl, ethyl, butyl, and ethoxycarbonyl.

根據本發明之某些實施方式，三芳基噌啉鹽化合物具有以下式(3)的結構：

Figure 02_image008
式(3)； 其中R 4選自由甲基、乙基、異丙基、叔丁基、甲氧基、三氟甲氧基、三氟甲基、乙醯基、氟、氯、及溴所組成的群組。 According to certain embodiments of the present invention, the triarylcinnoline salt compound has the structure of the following formula (3):
Figure 02_image008
Formula (3); wherein R 4 is selected from methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethoxy, trifluoromethyl, acetyl, fluorine, chlorine, and bromine formed group.

根據本發明之某些實施方式，三芳基噌啉鹽化合物具有以下式(4)的結構：

Figure 02_image010
式(4)； 其中R為氫或甲基；以及R’為氫或甲基，且R與R’不同。 According to certain embodiments of the present invention, the triarylcinnoline salt compound has the structure of the following formula (4):
Figure 02_image010
Formula (4); wherein R is hydrogen or methyl; and R' is hydrogen or methyl, and R is different from R'.

根據本發明之某些實施方式，三芳基噌啉鹽化合物具有以下式(5)的結構：

Figure 02_image012
式(5)； 其中R 5選自甲基、氟、氯、及氰基所組成的群組。 According to certain embodiments of the present invention, the triarylcinnoline salt compound has the structure of the following formula (5):
Figure 02_image012
Formula (5); wherein R 5 is selected from the group consisting of methyl, fluorine, chlorine, and cyano.

根據本發明之某些實施方式，三芳基噌啉鹽化合物具有以下式(6)的結構：

Figure 02_image014
式(6)； 其中環A選自由呋喃環、噻吩環、吲哚環及萘環所組成的群組。 According to certain embodiments of the present invention, the triarylcinnoline salt compound has the structure of the following formula (6):
Figure 02_image014
Formula (6); wherein Ring A is selected from the group consisting of furan ring, thiophene ring, indole ring and naphthalene ring.

根據本發明之各種實施方式，提供一種三芳基噌啉鹽化合物的製造方法，包括混合具有以下式(A)結構的2-偶氮二芳基化合物、具有以下式(B)結構的炔烴、釕金屬催化劑、氧化劑、反陰離子劑、脫氯劑、及有機溶劑，以形成混合物：

Figure 02_image016
式(A)，
Figure 02_image018
式(B)； 其中R 1選自由芳基、烷基、及乙氧羰基所組成的群組，R 2為芳基，R 3為氫或甲基，且環A為芳香環；將上述混合物置於約110 oC~140 oC下反應12~36小時，獲得如上述具有式(1)結構的三芳基噌啉鹽化合物。 According to various embodiments of the present invention, there is provided a method for producing a triarylcinnoline salt compound, comprising mixing a 2-azodiaryl compound having the structure of the following formula (A), an alkyne having the structure of the following formula (B), Ruthenium metal catalyst, oxidant, counter anion, dechlorination agent, and organic solvent to form a mixture:
Figure 02_image016
Formula (A),
Figure 02_image018
Formula (B); wherein R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl, R 2 is aryl, R 3 is hydrogen or methyl, and ring A is an aromatic ring; the above mixture is The reaction is carried out at about 110 o C to 140 o C for 12 to 36 hours to obtain the triarylcinnoline salt compound having the structure of formula (1) as above.

根據本發明之某些實施方式，其中R 1選自由以下基團所組成的群組：

Figure 02_image019
、
Figure 02_image020
、
Figure 02_image021
、
Figure 02_image022
、
Figure 02_image023
、
Figure 02_image024
、
Figure 02_image025
、
Figure 02_image026
、
Figure 02_image027
、
Figure 02_image028
、
Figure 02_image029
、苯基、乙基、丁基、及乙氧羰基，R 2選自由以下基團所組成的群組：
Figure 02_image019
、
Figure 02_image020
、
Figure 02_image021
、
Figure 02_image022
、
Figure 02_image023
、
Figure 02_image024
、
Figure 02_image025
、
Figure 02_image026
、
Figure 02_image027
、
Figure 02_image028
、
Figure 02_image029
、及苯基，其中*表示鍵結鍵，R 3為氫，且環A為苯環。 According to certain embodiments of the present invention, wherein R 1 is selected from the group consisting of:
Figure 02_image019
,
Figure 02_image020
,
Figure 02_image021
,
Figure 02_image022
,
Figure 02_image023
,
Figure 02_image024
,
Figure 02_image025
,
Figure 02_image026
,
Figure 02_image027
,
Figure 02_image028
,
Figure 02_image029
, phenyl, ethyl, butyl, and ethoxycarbonyl, and R 2 is selected from the group consisting of:
Figure 02_image019
,
Figure 02_image020
,
Figure 02_image021
,
Figure 02_image022
,
Figure 02_image023
,
Figure 02_image024
,
Figure 02_image025
,
Figure 02_image026
,
Figure 02_image027
,
Figure 02_image028
,
Figure 02_image029
, and phenyl, wherein * represents a bond, R 3 is hydrogen, and ring A is a benzene ring.

根據本發明之某些實施方式，其中R 1及R 2為苯基，R 3為氫或甲基，且環A為苯環或具有一取代基的苯環，其中取代基為甲基、氟、氯、或氰基。 According to certain embodiments of the present invention, wherein R 1 and R 2 are phenyl, R 3 is hydrogen or methyl, and Ring A is a benzene ring or a benzene ring with a substituent, wherein the substituent is methyl, fluorine , chlorine, or cyano.

根據本發明之某些實施方式，其中R 1及R 2為苯基，R 3為氫，且環A選自由呋喃環、噻吩環、吲哚環及萘環所組成的群組。 According to certain embodiments of the present invention, wherein R 1 and R 2 are phenyl, R 3 is hydrogen, and Ring A is selected from the group consisting of furan ring, thiophene ring, indole ring, and naphthalene ring.

根據本發明之某些實施方式，其中釕金屬催化劑為對傘花烴二氯化釕(II)二聚體，氧化劑為碳酸銀，且有機溶劑為三氟乙醇。According to certain embodiments of the present invention, the ruthenium metal catalyst is p-cymene dichloride ruthenium(II) dimer, the oxidant is silver carbonate, and the organic solvent is trifluoroethanol.

為了使本揭示內容的敘述更加詳盡與完備，下文針對了本發明的實施態樣與具體實施例提出了說明性的描述；但這並非實施或運用本發明具體實施例的唯一形式。以下所揭露的各實施例，在有益的情形下可相互組合或取代，也可在一實施例中附加其他的實施例，而無須進一步的記載或說明。In order to make the description of the present disclosure more detailed and complete, the following provides an illustrative description for the embodiments and specific embodiments of the present invention; but this is not the only form of implementing or using the specific embodiments of the present invention. The embodiments disclosed below can be combined or substituted with each other under beneficial circumstances, and other embodiments can also be added to one embodiment without further description or explanation.

於本文中，除非內文中對於冠詞有所特別限定，否則「一」與「該」可泛指單一個或多個。將進一步理解的是，本文中所使用之「包含」、「包括」、「具有」及相似詞彙，指明其所記載的特徵、區域、整數、步驟、操作、元件與/或組件，但不排除其所述或額外的其一個或多個其它特徵、區域、整數、步驟、操作、元件、組件，與/或其中之群組。As used herein, unless the context specifically defines the article, "a" and "the" can refer to a single or a plurality. It will be further understood that the words "comprising", "including", "having" and similar words used herein designate the recited features, regions, integers, steps, operations, elements and/or components, but do not exclude one or more of its other features, regions, integers, steps, operations, elements, components, and/or groups thereof, described or additional thereto.

本揭示之一態樣，提供一種三芳基噌啉鹽化合物，具有以下式(1)的結構：

Figure 02_image001
式(1)。 One aspect of the present disclosure provides a triarylcinnoline salt compound having the structure of the following formula (1):
Figure 02_image001
Formula 1).

在式(1)中，R 1選自由芳基、烷基、及乙氧羰基所組成的群組；R 2為芳基；R 3為氫或甲基；以及環A為芳香環。 In formula (1), R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl; R 2 is aryl; R 3 is hydrogen or methyl; and Ring A is an aromatic ring.

在一些實施方式中，三芳基噌啉鹽化合物具有以下式(2)的結構：

Figure 02_image006
式(2)。 In some embodiments, the triarylcinnoline salt compound has the structure of the following formula (2):
Figure 02_image006
Formula (2).

在式(2)中，R 1選自由苯基、乙基、丁基、及乙氧羰基所組成的群組。 具體而言，本揭示的三芳基噌啉鹽化合物可以具有如以下式(2-1)~式(2-4)所示的結構：

Figure 02_image032
式(2-1)、
Figure 02_image033
式(2-2)、
Figure 02_image034
式(2-3)、
Figure 02_image035
式(2-4)。 In formula (2), R 1 is selected from the group consisting of phenyl, ethyl, butyl, and ethoxycarbonyl. Specifically, the triarylcinnoline salt compound of the present disclosure may have the structures shown in the following formulas (2-1) to (2-4):
Figure 02_image032
Formula (2-1),
Figure 02_image033
Formula (2-2),
Figure 02_image034
Formula (2-3),
Figure 02_image035
Formula (2-4).

在一些實施方式中，三芳基噌啉鹽化合物具有以下式(3)的結構：

Figure 02_image008
式(3)。 In some embodiments, the triarylcinnoline salt compound has the following structure of formula (3):
Figure 02_image008
Formula (3).

在式(3)中，R 4選自由甲基、乙基、異丙基、叔丁基、甲氧基、三氟甲氧基、三氟甲基、乙醯基、氟、氯、及溴所組成的群組。 In formula ( 3 ), R4 is selected from methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethoxy, trifluoromethyl, acetyl, fluorine, chlorine, and bromine formed groups.

具體而言，本揭示的三芳基噌啉鹽化合物可以具有如以下式(3-1)~式(3-11)所示的結構：

Figure 02_image037
式(3-1)、
Figure 02_image038
式(3-2)、
Figure 02_image039
式(3-3)、
Figure 02_image040
式(3-4)、
Figure 02_image041
式(3-5)、
Figure 02_image042
式(3-6)、
Figure 02_image043
式(3-7)、
Figure 02_image044
式(3-8)、
Figure 02_image045
式(3-9)、
Figure 02_image046
式(3-10)、
Figure 02_image047
式(3-11)。 Specifically, the triarylcinnoline salt compound of the present disclosure may have the structures shown in the following formulas (3-1) to (3-11):
Figure 02_image037
Formula (3-1),
Figure 02_image038
Formula (3-2),
Figure 02_image039
Formula (3-3),
Figure 02_image040
Formula (3-4),
Figure 02_image041
Formula (3-5),
Figure 02_image042
Formula (3-6),
Figure 02_image043
Formula (3-7),
Figure 02_image044
Formula (3-8),
Figure 02_image045
Formula (3-9),
Figure 02_image046
Formula (3-10),
Figure 02_image047
Formula (3-11).

在一些實施方式中，三芳基噌啉鹽化合物具有以下式(4)的結構：

Figure 02_image010
式(4)。 In some embodiments, the triarylcinnoline salt compound has the following structure of formula (4):
Figure 02_image010
Formula (4).

在式(4)中，R為氫或甲基，R’為氫或甲基，且R與R’不同。In formula (4), R is hydrogen or methyl, R' is hydrogen or methyl, and R is different from R'.

具體而言，本揭示的三芳基噌啉鹽化合物可以具有如以下式(4-1)~式(4-2)所示的結構：

Figure 02_image049
式(4-1)、
Figure 02_image050
式(4-2)。 Specifically, the triarylcinnoline salt compound of the present disclosure may have the structures shown in the following formulas (4-1) to (4-2):
Figure 02_image049
Formula (4-1),
Figure 02_image050
Formula (4-2).

在一些實施方式中，三芳基噌啉鹽化合物具有以下式(5)的結構：

Figure 02_image012
式(5)。 In some embodiments, the triarylcinnoline salt compound has the structure of the following formula (5):
Figure 02_image012
Formula (5).

在式(5)中，R 5選自甲基、氟、氯、及氰基所組成的群組。 In formula (5), R 5 is selected from the group consisting of methyl, fluorine, chlorine, and cyano.

具體而言，本揭示的三芳基噌啉鹽化合物可以具有如以下式(5-1)~式(5-4)所示的結構：

Figure 02_image052
式(5-1)、
Figure 02_image053
式(5-2)、
Figure 02_image054
式(5-3)、
Figure 02_image055
式(5-4)。 Specifically, the triarylcinnoline salt compound of the present disclosure may have the structures shown in the following formulas (5-1) to (5-4):
Figure 02_image052
Formula (5-1),
Figure 02_image053
Formula (5-2),
Figure 02_image054
Formula (5-3),
Figure 02_image055
Formula (5-4).

在一些實施方式中，三芳基噌啉鹽化合物具有以下式(6)的結構：

Figure 02_image014
式(6)。 In some embodiments, the triarylcinnoline salt compound has the following structure of formula (6):
Figure 02_image014
Formula (6).

在式(6)中，環A選自呋喃環、噻吩環、吲哚環及萘環所組成的群組。In formula (6), ring A is selected from the group consisting of furan ring, thiophene ring, indole ring and naphthalene ring.

具體而言，本揭示的三芳基噌啉鹽化合物可以具有如以下式(6-1)~式(6-5)所示的結構：

Figure 02_image057
式(6-1)、
Figure 02_image058
式(6-2)、
Figure 02_image059
式(6-3)、
Figure 02_image060
式(6-4)、
Figure 02_image061
式(6-5)。 Specifically, the triarylcinnoline salt compound of the present disclosure may have the structures shown in the following formulas (6-1) to (6-5):
Figure 02_image057
Formula (6-1),
Figure 02_image058
Formula (6-2),
Figure 02_image059
Formula (6-3),
Figure 02_image060
Formula (6-4),
Figure 02_image061
Formula (6-5).

對上述式(3-3)、式(3-6)、式(4-1)、式(5-2)、式(6-1)、式(6-2)所示的三芳基噌啉鹽化合物進行吸收及螢光測試（1.0 ×10 -5M，激發波長 290 nm，在二氯甲烷中），結果分別如第1圖及第2圖所示。 For the triarylcinnoline represented by the above formula (3-3), formula (3-6), formula (4-1), formula (5-2), formula (6-1) and formula (6-2) The salt compounds were tested for absorption and fluorescence (1.0 × 10 -5 M, excitation wavelength 290 nm, in dichloromethane), and the results are shown in Figures 1 and 2, respectively.

請參考第1圖及第2圖。這些三芳基噌啉鹽化合物顯示強吸收(π-π*)帶，在波長430 nm至540 nm之間具有最大吸收波峰。上述三芳基噌啉鹽化合物被激發後，在波長540-700 nm之間具有最大螢光放光，且具有寬帶寬(bandwidth)及高強度。根據三芳基噌啉鹽化合物上取代基的不同，呈現綠色至紫色的螢光。與其他三芳基噌啉鹽化合物相比，式(6-1)及式(6-2)所示的三芳基噌啉鹽化合物的吸收光譜及螢光光譜分別紅移約168 nm及111 nm。此外，由於芳香環的π–π*躍遷，第1圖及第2圖中所示的三芳基噌啉鹽化合物皆顯示出較大的斯托克斯位移(Stokes shift)，造成螢光淬滅(quenching)的消除及較強的訊號。Please refer to Figure 1 and Figure 2. These triarylcinnoline salt compounds show strong absorption (π-π*) bands with absorption maxima between 430 nm and 540 nm. After the above-mentioned triarylcinnoline salt compound is excited, it has a maximum fluorescence emission at a wavelength of 540-700 nm, and has a wide bandwidth and high intensity. Depending on the substituent on the triarylcinnoline salt compound, it exhibits green to purple fluorescence. Compared with other triarylcinnoline salt compounds, the absorption spectrum and fluorescence spectrum of the triarylcinnoline salt compounds represented by formula (6-1) and formula (6-2) are red-shifted by about 168 nm and 111 nm, respectively. In addition, due to the π–π* transition of the aromatic ring, the triarylcinnoline compounds shown in Figure 1 and Figure 2 both show a large Stokes shift, resulting in fluorescence quenching (quenching) elimination and stronger signal.

本揭示的三芳基噌啉鹽化合物在各種有機溶劑中具有良好的溶解性，並顯示出最大螢光放光波長在525 nm至693 nm的範圍內，且具有寬帶寬。本揭示的三芳基噌啉鹽化合物可用於亮綠色、黃色、橙色、橙紅色及深紫色溶液製程的 OLED 材料。The triarylcinnoline salt compound of the present disclosure has good solubility in various organic solvents, and exhibits a maximum fluorescence emission wavelength in the range of 525 nm to 693 nm, and has a wide bandwidth. The triarylcinnoline salt compounds of the present disclosure can be used for OLED materials in bright green, yellow, orange, orange-red and deep violet solution processes.

本揭示之另一態樣，提供一種三芳基噌啉鹽化合物的製造方法，包括以下步驟。混合具有以下式(A)結構的2-偶氮二芳基化合物、具有以下式(B)結構的炔烴、釕金屬催化劑、氧化劑、反陰離子劑(counter anion reagent) 脫氯劑、及有機溶劑，以形成混合物：

Figure 02_image016
式(A)，
Figure 02_image018
式(B)； 其中R 1選自由芳基、烷基、及乙氧羰基所組成的群組，R 2為芳基，R 3為氫或甲基，且環A為芳香環。在一些實施方式中，R 1與R 2為相同的基團。在其他實施方式中，R 1與R 2為不同的基團。 Another aspect of the present disclosure provides a method for producing a triarylcinnoline salt compound, comprising the following steps. A 2-azodiaryl compound having the structure of the following formula (A), an alkyne having the structure of the following formula (B), a ruthenium metal catalyst, an oxidizing agent, a counter anion reagent, a dechlorination agent, and an organic solvent are mixed , to form the mixture:
Figure 02_image016
Formula (A),
Figure 02_image018
Formula (B); wherein R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl, R 2 is aryl, R 3 is hydrogen or methyl, and ring A is an aromatic ring. In some embodiments, R 1 and R 2 are the same group. In other embodiments, R 1 and R 2 are different groups.

在一些實施方式中，R 1選自由以下基團所組成的群組：

Figure 02_image019
、
Figure 02_image020
、
Figure 02_image021
、
Figure 02_image022
、
Figure 02_image023
、
Figure 02_image024
、
Figure 02_image025
、
Figure 02_image026
、
Figure 02_image027
、
Figure 02_image028
、
Figure 02_image029
、苯基、乙基、丁基、及乙氧羰基，R 2選自由以下基團所組成的群組:
Figure 02_image019
、
Figure 02_image020
、
Figure 02_image021
、
Figure 02_image022
、
Figure 02_image023
、
Figure 02_image024
、
Figure 02_image025
、
Figure 02_image026
、
Figure 02_image027
、
Figure 02_image028
、
Figure 02_image029
、及苯基，其中*表示鍵結鍵；R 3為氫，且環A為苯環。 In some embodiments, R 1 is selected from the group consisting of:
Figure 02_image019
,
Figure 02_image020
,
Figure 02_image021
,
Figure 02_image022
,
Figure 02_image023
,
Figure 02_image024
,
Figure 02_image025
,
Figure 02_image026
,
Figure 02_image027
,
Figure 02_image028
,
Figure 02_image029
, phenyl, ethyl, butyl, and ethoxycarbonyl, R 2 is selected from the group consisting of:
Figure 02_image019
,
Figure 02_image020
,
Figure 02_image021
,
Figure 02_image022
,
Figure 02_image023
,
Figure 02_image024
,
Figure 02_image025
,
Figure 02_image026
,
Figure 02_image027
,
Figure 02_image028
,
Figure 02_image029
, and phenyl, wherein * represents a bonding bond; R 3 is hydrogen, and ring A is a benzene ring.

在一些實施方式中，R 1及R 2為苯基，R 3為氫或甲基，且環A為苯環或具有一取代基的苯環，其中上述取代基為甲基、氟、氯、或氰基。 In some embodiments, R 1 and R 2 are phenyl, R 3 is hydrogen or methyl, and Ring A is a benzene ring or a benzene ring with a substituent, wherein the substituents are methyl, fluorine, chlorine, or cyano.

在一些實施方式中，在反應式(A)中，R 1及R 2為苯基，R 3為氫，且環A選自由呋喃環、噻吩環、吲哚環及萘環所組成的群組。 In some embodiments, in formula (A), R 1 and R 2 are phenyl, R 3 is hydrogen, and ring A is selected from the group consisting of furan ring, thiophene ring, indole ring, and naphthalene ring .

在一些實施方式中，釕金屬催化劑為對傘花烴二氯化釕(II)二聚體 [Ru( p-cymene)Cl 2] 2。在一些實施方式中，氧化劑為碳酸銀。在一些實施方式中，反陰離子劑包括四氟硼酸鈉、六氟磷酸鈉或三氟磺酸鈉。在一些實施方式中，脫氯劑包括四氟硼酸銀、六氟磷酸銀或硝酸銀。在一些實施方式中，有機溶劑為三氟乙醇。 In some embodiments, the ruthenium metal catalyst is p-cymene ruthenium(II) dichloride dimer [Ru( p -cymene )Cl2]2 . In some embodiments, the oxidizing agent is silver carbonate. In some embodiments, the counter-anion agent includes sodium tetrafluoroborate, sodium hexafluorophosphate, or sodium trifluorosulfonate. In some embodiments, the dechlorination agent includes silver tetrafluoroborate, silver hexafluorophosphate, or silver nitrate. In some embodiments, the organic solvent is trifluoroethanol.

之後，將上述混合物置於約110 oC~140 oC下反應12~36小時獲得如上述具有式(1)結構的三芳基噌啉鹽化合物。在一些實施方式中，反應溫度為120 oC。在一些實施方式中，上述混合物在氮氣環境下反應24小時，接著冷卻至室溫並純化後獲得三芳基噌啉鹽化合物。 After that, the above mixture is placed at about 110 o C to 140 o C and reacted for 12 to 36 hours to obtain the triarylcinnoline salt compound having the structure of formula (1) as described above. In some embodiments, the reaction temperature is 120 ° C. In some embodiments, the above mixture is reacted under nitrogen atmosphere for 24 hours, then cooled to room temperature and purified to obtain the triarylcinnoline salt compound.

具體而言，以2-偶氮二芳基(2-azo-biaryls)化合物及炔烴(或炔烴衍生物)作為反應物，利用釕金屬催化劑催化碳氫(C-H) 鍵活化及偶氮苯和內部炔烴的環化來製備綠色至紫色螢光三芳基噌啉鹽化合物。Specifically, 2-azo-biaryls (2-azo-biaryls) compounds and alkynes (or alkyne derivatives) are used as reactants, and ruthenium metal catalysts are used to catalyze hydrocarbon (C-H) bond activation and azobenzene and cyclization of internal alkynes to prepare green to violet fluorescent triarylcinnoline compounds.

舉例而言，前述式(2-1)所示的三芳基噌啉鹽化合物的製造方法可以由以下反應式表示：

Figure 02_image062
For example, the production method of the triarylcinnoline salt compound represented by the aforementioned formula (2-1) can be represented by the following reaction formula:
Figure 02_image062

如上反應式所示，在耐壓試管中加入標記為1a的2-偶氮二芳基化合物(0.1 mmol，33.4 mg)、標記為2a的二苯乙炔(diphenylacetylene，0.15 mmol)、釕催化劑[Ru( p-cymene)Cl 2] 2(10 mol%)、碳酸銀(Ag 2CO 3，0.2 mmol，55 mg)以及四氟硼酸鈉(NaBF 4，0.2 mmol，22 mg)後，將耐壓試管放入手套箱(glove box)中。之後，將四氟硼酸銀(AgBF 4)(20 mol %)及三氟乙醇(triflouroethanol，TFE，1.5 mL)加入上述試管中。接著密封試管並將其從手套箱中取出，在120 oC下攪拌24小時。 As shown in the above reaction formula, 2-azodiaryl compound labeled 1a (0.1 mmol, 33.4 mg), diphenylacetylene (0.15 mmol) labeled 2a, ruthenium catalyst [Ru ( p -cymene)Cl 2 ] 2 (10 mol%), silver carbonate (Ag 2 CO 3 , 0.2 mmol, 55 mg) and sodium tetrafluoroborate (NaBF 4 , 0.2 mmol, 22 mg), a pressure-resistant test tube was added. Put in the glove box. After that, silver tetrafluoroborate (AgBF 4 ) (20 mol %) and trifluoroethanol (TFE, 1.5 mL) were added to the above test tube. The tube was then sealed and removed from the glove box and stirred at 120 ° C for 24 hours.

當反應完成後，將殘餘物冷卻至室溫，並以二氯甲烷(15mL)作為沖提液通過矽藻土墊(Celite pad)過濾。之後，濃縮濾液並以矽膠管柱層析進一步純化(MeOH/EtOAc 20/80)以獲得式(2-1)所示的三芳基噌啉鹽化合物(在上式中標記為3aa)。When the reaction was complete, the residue was cooled to room temperature and filtered through a Celite pad with dichloromethane (15 mL) as eluent. After that, the filtrate was concentrated and further purified by silica gel column chromatography (MeOH/EtOAc 20/80) to obtain the triarylcinnoline salt compound represented by formula (2-1) (marked as 3aa in the above formula).

上述標記為3aa的三芳基噌啉鹽化合物其性質量測結果如下。黃色固體；熔點158~162 °C； 1H NMR (400 MHz, CDCl 3): δ 8.41 (d, J= 7.9 Hz, 1H), 8.19-8.12 (m, 2H), 7.89 (d, J= 7.4 Hz, 2H), 7.77 (d, J= 8.2 Hz, 1H), 7.56-7.53 (m, 4H), 7.50-7.44 (m, 2H), 7.35-7.30 (m, 3H), 7.23-7.17 (m, 3H), 7.14-7.05 (m, 4H), 7.00 (d, J= 7.1 Hz, 1H), 6.75 (t, J= 7.5 Hz, 1H), 6.51 (d, J= 7.6 Hz, 2H), 5.71 (d, J= 7.8 Hz, 1H); 13C NMR (100 MHz, CDCl 3): δ 152.1, 147.9, 146.7, 143.5, 142.9, 138.3, 136.3, 135.9, 135.5, 135.2, 132.1, 131.3, 131.26, 131.2, 131.1, 130.6, 130.1, 129.7, 129.5, 129.3, 129.2, 129.09, 129.05, 129.0, 128.9, 128.8, 128.5, 128.4, 128.2, 128.0, 127.5, 126.6, 125.3; HRMS (ESI+): [C 38H 27N 2] +計算值511.2174，實測值511.2182; IR (KBr): 3057, 1599, 1534, 1056 ( ν B -F) cm -1。 The properties and mass measurement results of the triarylcinnoline salt compound marked as 3aa are as follows. Yellow solid; melting point 158~162 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 8.41 (d, J = 7.9 Hz, 1H), 8.19-8.12 (m, 2H), 7.89 (d, J = 7.4 Hz, 2H), 7.77 (d, J = 8.2 Hz, 1H), 7.56-7.53 (m, 4H), 7.50-7.44 (m, 2H), 7.35-7.30 (m, 3H), 7.23-7.17 (m, 3H), 7.14-7.05 (m, 4H), 7.00 (d, J = 7.1 Hz, 1H), 6.75 (t, J = 7.5 Hz, 1H), 6.51 (d, J = 7.6 Hz, 2H), 5.71 ( d, J = 7.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 152.1, 147.9, 146.7, 143.5, 142.9, 138.3, 136.3, 135.9, 135.5, 135.2, 132.1, 131.3, 131. 131.1, 130.6, 130.1, 129.7, 129.5, 129.3, 129.2, 129.05, 129.0, 128.9, 128.8, 128.4, 128.2, 127.5, 126.6, 125.3; HRMS (ESI+): [C 38 H 27 N 2 2 2 2 2 2 ] + calcd 511.2174, found 511.2182; IR (KBr): 3057, 1599, 1534, 1056 ( ν B -F ) cm -1 .

如上所述，本揭示的三芳基噌啉鹽化合物在各種有機溶劑中具有良好的溶解性，具有大斯托克斯位移和近紅外螢光的綠色至紫色螢光，可用於溶液製程的 OLED 材料。此外，本揭示利用2-偶氮二芳基化合物、炔烴及釕金屬催化劑製備三芳基噌啉鹽化合物。與現有技術(例如，使用鈀或銠金屬催化)相比，本揭示提供一種效率較高且成本較低的製備方法。As mentioned above, the triarylcinnoline salt compounds of the present disclosure have good solubility in various organic solvents, green to violet fluorescence with large Stokes shift and near-infrared fluorescence, and can be used in solution-processed OLED materials . In addition, the present disclosure utilizes 2-azodiaryl compounds, alkynes and ruthenium metal catalysts to prepare triarylcinnoline compounds. The present disclosure provides a higher efficiency and lower cost preparation method than the prior art (eg, using palladium or rhodium metal catalysis).

雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be determined by the scope of the appended patent application.

無none

當讀到隨附的圖式時，從以下詳細的敘述可充分瞭解本揭露的各方面。 第1圖為光吸收測試結果。 第2圖為螢光測試結果。Aspects of the present disclosure can be fully understood from the following detailed description when reading the accompanying drawings. Figure 1 shows the results of the light absorption test. Figure 2 shows the results of the fluorescence test.

國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無 Domestic storage information (please note in the order of storage institution, date and number) none Foreign deposit information (please note in the order of deposit country, institution, date and number) none

Figure 01_image001
Figure 01_image001

Claims (11)

一種三芳基噌啉鹽化合物，具有以下式(1)的結構：
Figure 03_image001
式(1)； 其中R 1選自由芳基、烷基、及乙氧羰基所組成的群組； R 2為芳基； R 3為氫或甲基；以及 環A為芳香環。 A triaryl cinnoline salt compound has the structure of the following formula (1):
Figure 03_image001
Formula (1); wherein R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl; R 2 is aryl; R 3 is hydrogen or methyl; and Ring A is an aromatic ring. 如請求項1所述之三芳基噌啉鹽化合物，具有以下式(2)的結構：
Figure 03_image006
式(2)； 其中R 1選自由苯基、乙基、丁基、及乙氧羰基所組成的群組。 The triarylcinnoline salt compound according to claim 1 has the structure of the following formula (2):
Figure 03_image006
Formula (2); wherein R 1 is selected from the group consisting of phenyl, ethyl, butyl, and ethoxycarbonyl. 如請求項1所述之三芳基噌啉鹽化合物，具有以下式(3)的結構：
Figure 03_image008
式(3)； 其中R 4選自由甲基、乙基、異丙基、叔丁基、甲氧基、三氟甲氧基、三氟甲基、乙醯基、氟、氯、及溴所組成的群組。 The triarylcinnoline salt compound according to claim 1 has the structure of the following formula (3):
Figure 03_image008
Formula (3); wherein R 4 is selected from methyl, ethyl, isopropyl, tert-butyl, methoxy, trifluoromethoxy, trifluoromethyl, acetyl, fluorine, chlorine, and bromine formed group. 如請求項1所述之三芳基噌啉鹽化合物，具有以下式(4)的結構：
Figure 03_image010
式(4)； 其中R為氫或甲基；以及 R’為氫或甲基，且R與R’不同。 The triarylcinnoline salt compound according to claim 1 has the structure of the following formula (4):
Figure 03_image010
Formula (4); wherein R is hydrogen or methyl; and R' is hydrogen or methyl, and R is different from R'. 如請求項1所述之三芳基噌啉鹽化合物，具有以下式(5)的結構：
Figure 03_image012
式(5)； 其中R 5選自甲基、氟、氯、及氰基所組成的群組。 The triarylcinnoline salt compound according to claim 1 has the structure of the following formula (5):
Figure 03_image012
Formula (5); wherein R 5 is selected from the group consisting of methyl, fluorine, chlorine, and cyano. 如請求項1所述之三芳基噌啉鹽化合物，具有以下式(6)的結構：
Figure 03_image014
式(6)； 其中環A選自呋喃環、噻吩環、吲哚環及萘環所組成的群組。 The triarylcinnoline salt compound according to claim 1 has the structure of the following formula (6):
Figure 03_image014
Formula (6); wherein Ring A is selected from the group consisting of furan ring, thiophene ring, indole ring and naphthalene ring. 一種三芳基噌啉鹽化合物的製造方法，包括： 混合具有以下式(A)結構的2-偶氮二芳基化合物、具有以下式(B)結構的炔烴、一釕金屬催化劑、一氧化劑、反陰離子劑、脫氯劑、及一有機溶劑，以形成一混合物：
Figure 03_image016
式(A)，
Figure 03_image018
式(B)； 其中R 1選自由芳基、烷基、及乙氧羰基所組成的群組，R 2為芳基，R 3為氫或甲基，且環A為芳香環； 將該混合物置於約110 oC~140 oC下反應12~36小時，獲得如請求項1所述之具有式(1)結構的三芳基噌啉鹽化合物。 A method for producing a triarylcinnoline salt compound, comprising: mixing a 2-azodiaryl compound having the structure of the following formula (A), an alkyne having the structure of the following formula (B), a ruthenium metal catalyst, an oxidizing agent, a counter-anion agent, a dechlorination agent, and an organic solvent to form a mixture:
Figure 03_image016
Formula (A),
Figure 03_image018
formula (B); wherein R 1 is selected from the group consisting of aryl, alkyl, and ethoxycarbonyl, R 2 is aryl, R 3 is hydrogen or methyl, and ring A is an aromatic ring; the mixture The reaction is carried out at about 110 o C to 140 o C for 12 to 36 hours to obtain the triarylcinnoline salt compound having the structure of formula (1) as described in claim 1. 如請求項7的製造方法，其中R 1選自由以下基團所組成的群組：
Figure 03_image019
、
Figure 03_image020
、
Figure 03_image021
、
Figure 03_image022
、
Figure 03_image023
、
Figure 03_image024
、
Figure 03_image025
、
Figure 03_image026
、
Figure 03_image027
、
Figure 03_image028
、
Figure 03_image029
、苯基、乙基、丁基、及乙氧羰基； R 2選自由以下基團所組成的群組： 苯基、
Figure 03_image019
、
Figure 03_image020
、
Figure 03_image021
、
Figure 03_image022
、
Figure 03_image023
、
Figure 03_image024
、
Figure 03_image025
、
Figure 03_image026
、
Figure 03_image027
、
Figure 03_image028
、及
Figure 03_image029
，其中*表示鍵結鍵；以及 R 3為氫，且環A為苯環。 The manufacturing method of claim 7, wherein R 1 is selected from the group consisting of:
Figure 03_image019
,
Figure 03_image020
,
Figure 03_image021
,
Figure 03_image022
,
Figure 03_image023
,
Figure 03_image024
,
Figure 03_image025
,
Figure 03_image026
,
Figure 03_image027
,
Figure 03_image028
,
Figure 03_image029
, phenyl, ethyl, butyl, and ethoxycarbonyl; R 2 is selected from the group consisting of: phenyl,
Figure 03_image019
,
Figure 03_image020
,
Figure 03_image021
,
Figure 03_image022
,
Figure 03_image023
,
Figure 03_image024
,
Figure 03_image025
,
Figure 03_image026
,
Figure 03_image027
,
Figure 03_image028
,and
Figure 03_image029
, where * represents a bonding bond; and R 3 is hydrogen, and Ring A is a benzene ring. 如請求項7的製造方法，其中R 1及R 2為苯基，R 3為氫或甲基，且環A為苯環或具有一取代基的苯環，其中該取代基為甲基、氟、氯、或氰基。 The production method of claim 7, wherein R 1 and R 2 are phenyl groups, R 3 is hydrogen or methyl, and ring A is a benzene ring or a benzene ring with a substituent, wherein the substituent is methyl, fluorine , chlorine, or cyano. 如請求項7的製造方法，其中R 1及R 2為苯基，R 3為氫，且環A選自由呋喃環、噻吩環、吲哚環及萘環所組成的群組。 The production method according to claim 7, wherein R 1 and R 2 are phenyl groups, R 3 is hydrogen, and ring A is selected from the group consisting of furan ring, thiophene ring, indole ring and naphthalene ring. 如請求項7的製造方法，其中該釕金屬催化劑為對傘花烴二氯化釕(II)二聚體，該氧化劑為碳酸銀，且該有機溶劑為三氟乙醇。The manufacturing method of claim 7, wherein the ruthenium metal catalyst is a ruthenium(II) dichloride dimer of p-cymene, the oxidant is silver carbonate, and the organic solvent is trifluoroethanol.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101166730A (en) * 2005-03-01 2008-04-23 惠氏公司 Cinnoline compounds and their use as liver X receptor modilators
TW202108580A (en) * 2019-08-30 2021-03-01 國立交通大學 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101166730A (en) * 2005-03-01 2008-04-23 惠氏公司 Cinnoline compounds and their use as liver X receptor modilators
TW202108580A (en) * 2019-08-30 2021-03-01 國立交通大學 11-arylcinnolino[2,3-f]phenanthridin-9-ium salts and the manufacturing method thereof

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