- Expanding the hole delocalization range in excited molecules for stable organic light-emitting diodes employing thermally activated delayed fluorescence
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Metal-free, thermally activated delayed fluorescent (TADF) emitters have emerged as a promising new generation of organic light-emitting diode (OLED) materials. Donor-acceptor (D-A) structures are widely used in TADF molecular design to ensure a small energy splitting between the singlet and triplet excitons. Here, a series of efficient bluish-green TADF emitters are constructed using one or two phenyltriazine acceptors and one tercarbazole, bicarbazole or indolo[2,3-b]carbazole donor through an ortho-linkage. The impact of the D/A ratio on the photoluminescence and electroluminescence stability of these emitters in doped films is thoroughly investigated. According to the two-exciton dynamics and the degradation products, device degradation is deduced to be a result of electrophilic substitution between two charge-transfer excitons. Within a limited molecular weight range, increasing the number of acceptor moieties leads to a decrease in the hole delocalization range in the excited state, which facilitates the substitution reaction. Based on an optimized device structure, the device containing an emitter with bulk a tercarbazole donor achieves a long half-life of 1512 hours with an initial luminescence of 1000 cd m-2. Our findings reveal a possible mechanism for exciton-exciton and exciton-polaron annihilation-induced device degradation and provide new approaches for achieving stable OLEDs employing TADF.
- Ai, Qi,Cao, Fangyi,Deng, Chao,Liu, Zhang,Su, Liwu,Tsuboi, Taiju,Wang, Chao,Wang, Dan,Zhang, Qisheng,Zheng, Xinyuan,Zhu, Yunhui
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- Synthesis of 1,2-dihydro-1,3,5-triazine derivativesviaCu(ii)-catalyzed C(sp3)-H activation ofN,N-dimethylethanolamine with amidines
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1,2-Dihydro-1,3,5-triazines and symmetrical 1,3,5-triazines were obtained in up to 81% yields from amidines andN,N-dimethylethanolamine catalyzed by CuCl2. The reaction involves three C-N bond formations during the oxidative annulation process
- Chen, Rener,Ma, Renchao,Ma, Yongmin,Wang, Lei,Wang, Zhiming,Yan, Min
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supporting information
p. 10946 - 10949
(2020/10/02)
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- Dichloromethane as C1 Building Block: Synthesis of 2,4-Disubstitued 1,3,5-Triazines via Copper-Catalyzed Aerobic C?H/C?Cl Cleavage
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A copper-catalyzed aerobic oxidative annulation of amidines with dichloromethane was first demonstrated. Using this novel approach, 16 examples of symmetrical 2,4-disubstitued 1,3,5-triazines and 7 examples of unsymmetrical ones were obtained with up to 82% yields. Moreover, a D-labeling experiment proved that dichloromethane was employed as the C1 building block and solvent. A primary kinetic isotope effect revealed that the C?H cleavage of dichloromethane might be a rate-determining step. This protocol provides a novel strategy for the synthesis of heterocycles. (Figure presented.).
- Yan, Yizhe,Cui, Chang,Wang, Jianyong,Li, Shaoqing,Liu, Yanqi
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supporting information
p. 1166 - 1170
(2019/01/30)
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- New Strategy for the Synthesis of Heterocycles via Copper-Catalyzed Oxidative Decarboxylative Amination of Glyoxylic Acid
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A copper-catalyzed oxidative decarboxylative amination of glyoxylic acid with substrates having two nitrogen-nucleophilic sites was first demonstrated. Using this novel approach, 1,3,5-triazines, quinazolinones and quinazolines were obtained in up to 93 % yields. Notably, glyoxylic acid was employed as the C1 synthon for heterocycles. This strategy enriches the application of glyoxylic acid for the synthesis of valuable heterocycles.
- Niu, Bin,Li, Shaoqing,Cui, Chang,Yan, Yizhe,Tang, Lin,Wang, Jianyong
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supporting information
p. 7800 - 7803
(2019/11/28)
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- Transition metal-free C-F/C-Cl/C-C cleavage of ClCF2COONa for the synthesis of heterocycles
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A transition metal-free and external oxidant-free annulation of substrates having two nitrogen-nucleophilic sites with ClCF2COONa was demonstrated, affording a series of 1,3,5-triazines and quinazolinones in up to 96% yields. Notably, ClCF
- Yan, Yizhe,Cui, Chang,Wang, Jianyong,Li, Shaoqing,Tang, Lin,Liu, Yanqi
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supporting information
p. 8071 - 8074
(2019/09/19)
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- Transition metal-free assembly of 1,3,5-triazines using ethyl bromodifluoroacetate as C1 source
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An efficient transition metal-free annulation of amidine with ethyl bromodifluoroacetate to access 2,4-disubstituted-1,3,5-triazines is firstly presented. The desired symmetric and unsymmetric 2,4-disubstituted-1,3,5-triazines were obtained in decent yields via multiple C-N bond formation, in which ethyl bromodifluoroacetate is harnessed as a unique C1 synthon via quadruple cleavage. This reaction is transition metal-free, oxidant-free and simple in operation, and only lowly toxic inorganic wastes are generated.
- Yu, Xiaoxia,Zhou, Yao,Ma, Xingxing,Song, Qiuling
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supporting information
p. 8079 - 8082
(2019/07/15)
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- A multi-substituted 1, 3, 5 - triazine (by machine translation)
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The present invention discloses a multi-substituted 1, 3, 5 - triazine, in particular to in order to replace the carboxamidine hydrochloride as a reaction substrate, two fluorine chlorine sodium acetate as a carbon synthons, in the equivalent function of
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Paragraph 0019-0042
(2019/06/07)
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- An I2-mediated aerobic oxidative annulation of amidines with tertiary amines: Via C-H amination/C-N cleavage for the synthesis of 2,4-disubstituted 1,3,5-triazines
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An iodine-mediated formal oxidative cycloaddition of amidines with tertiary amines was first demonstrated in air. Both symmetrical and unsymmetrical 2,4-disubstituted 1,3,5-triazines were obtained in up to 85% yields. It is noted that a tertiary amine was employed as a one carbon synthon of 1,3,5-triazines and two C-N bonds were formed in one pot. Control experiments revealed that the reaction underwent a radical pathway promoted by I+. The method is transition-metal-free, peroxide-free, and operationally simple to implement with a wide scope of substrates.
- Yan, Yizhe,Li, Zheng,Cui, Chang,Li, Hongyi,Shi, Miaomiao,Liu, Yanqi
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supporting information
p. 2629 - 2633
(2018/04/27)
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- Silver-catalyzed [3+2+1] annulation of aryl amidines with benzyl isocyanide
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A silver-catalyzed [3+2+1] annulation of amidines with benzyl isocyanide toward 2,4-diaryl-1,3,5-triazines was developed. A variety of symmetrical and unsymmetrical products were obtained in moderate to good yields. This work also features an oxidant-free approach to 2,4-disubstituted triazines.
- Lu, Xiaodong,Xin, Xiaoyi,Wan, Boshun
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supporting information
p. 361 - 364
(2018/01/08)
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- Alkyl Ether as a One-Carbon Synthon: Route to 2,4-Disubstituted 1,3,5-Triazines via C-H Amination/C-O Cleavage under Transition-Metal-Free Conditions
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A transition-metal-free oxidative formal [3 + 2 + 1] cycloaddition for the synthesis of symmetrical and unsymmetrical 2,4-disubstituted 1,3,5-triazines has been first demonstrated. The reaction is involved in a domino C-H amination of alkyl ethers with amidines, C-O cleavage, nucleophilic addition, condensation, and an oxidative aromatization process. Notably, two C-N bonds were constructed in one pot, and alkyl ethers were employed as a novel carbon source of 1,3,5-triazines. The preliminary mechanistic studies revealed the reaction underwent a radical pathway.
- Yan, Yizhe,Li, Zheng,Li, Hongyi,Cui, Chang,Shi, Miaomiao,Liu, Yanqi
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supporting information
p. 6228 - 6231
(2017/11/24)
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- Preparation method for 2,4-disubstituted-1,3,5-triazine derivatives
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The invention relates to a preparation method for symmetric and asymmetric 2,4-disubstituted-1,3,5-triazine derivatives. Specifically, substituted amidine reacts with benzyl isocyanide under the catalysis of a silver salt or copper salt so as to produce t
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Paragraph 0014-0017; 0029-0032
(2017/07/20)
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- Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides
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Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.
- You, Qing,Wang, Fei,Wu, Chaoting,Shi, Tianchao,Min, Dewen,Chen, Huajun,Zhang, Wu
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supporting information
p. 6723 - 6727
(2015/06/25)
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- Copper-Catalyzed Oxidative C(sp3)-H Functionalization for Facile Synthesis of 1,2,4-Triazoles and 1,3,5-Triazines from Amidines
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A facile and versatile catalytic system involving copper catalyst, K3PO4 as the base, and O2 as the oxidant has been developed to enable efficient synthesis of 2,4,6-trisubstituted and 2,6-disubstituted 1,3,5-triazines and
- Huang, Huawen,Guo, Wei,Wu, Wanqing,Li, Chao-Junx,Jiang, Huanfeng
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supporting information
p. 2894 - 2897
(2015/06/30)
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- A novel straightforward synthesis of 2,4-disubstituted-1,3,5-triazines via aerobic copper-catalyzed cyclization of amidines with DMF
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A novel straightforward synthesis of both symmetrical and unsymmetrical 2,4-disubstituted-1,3,5-triazines via aerobic copper-catalyzed cyclization of amidines with DMF as a one-carbon synthon has been developed. The presented method allows synthesizing the products that are currently inaccessible or challenging to prepare with the advantages of operational simplicity, broad substrate scope, and no need for prefunctionalized reagents, making it a highly practical approach to access various 2,4-disubstituted-1,3,5-triazines.
- Xu, Xiaowen,Zhang, Min,Jiang, Huanfeng,Zheng, Jia,Li, Yiqun
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supporting information
p. 3540 - 3543
(2014/07/21)
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- Light-Emitting Device, Electronic Device, and Lighting Device Utilizing Phosphorescence
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A new light-emitting device utilizing phosphorescence is provided. Further, an electronic device and a lighting device which utilize phosphorescence are provided. One embodiment of the present invention is a light-emitting device including a phosphorescen
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Page/Page column 31
(2012/11/08)
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- Organometallic Complex, Light-Emitting Element, Light-Emitting Device, Electronic Device, and Lighting Device
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A novel organometallic complex which can emit phosphorescence is provided. A light-emitting element, a light-emitting device, an electronic device, or a lighting device with high emission efficiency is provided. The organometallic complex having an aryl triazine derivative as a ligand is represented by General Formula (G1) below as a representative of the organometallic complex of the present invention.
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Page/Page column 25-26
(2012/11/08)
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- Photochemistry of phenyl-substituted 1,2,4-thiadiazoles. 15N-labeling studies
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Irradiation of 5-phenyl-1,2,4-thiadiazole (6) resulted in the formation of benzonitrile (5), 3-phenyl-1,2,4-thiadiazole (4), phenyl- and diphenyl-1,3,5-triazines (7 and 8), and a trace quantity of diphenyl-1,2,4-thiadiazole (9). The formation of 4, 5, 7, and 8 can be explained in terms of photoinduced electrocyclic ring closure resulting in the formation of an intermediate 4-phenyl-1,3-diaza-5-thiabicyclo[2.1.0]pentene. 15N-labeling experiments revealed that sulfur can undergo sigmatropic shifts around all four sides of the diazetine ring. Thus, irradiation of 6-4-15N led to the formation of 6-2-15N and an equimolar mixture of 4-2-15N and 4-4-15N. The thiabicyclo[2.1.0]pentene intermediate is also suggested to undergo sulfur elimination resulting in the formation of phenyldiazacyclobutadiene, which can undergo complete fragmentation to benzonitrile or [4+2] cycloaddition leading to unstable tricyclic adducts, the suggested precursors of the 1,3,5-triazine products 7 and 8. The observed 15N distribution in 7 and 8 is consistent with this mechanism. Irradiation of 4 led only to the formation of 5. 15N-labeling experiments show that 4 does not undergo electrocyclic ring closure but reacts exclusively by photofragmentation of the thiadiazole ring.
- Pavlik, James W.,Changtong, Chuchawin,Vikki
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p. 4855 - 4861
(2007/10/03)
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- 1,3-Diaza-1,3-butadienes. Synthesis and conversion into pyrimidines by [4π + 2π] cycloaddition with electron deficient acetylenes. Synthetic utility of 2-(trichloromethyl)pyrimidines
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Methods have been devised to generate 1H-1,3-diaza-1,3-butadienes bearing a leaving group at position-4 in latent, masked, and unprotected forms. A hallmark of these azadienes is that they undergo thermal [4π ± 2π] cycloaddition reactions with electron deficient acetylenes to give adducts which are aromatized to pyrimidine derivatives under the reaction conditions. Thus, 1-(methoxycarbonyl)-3-acylamidines 17 on heating in solution are converted in situ into the 1,3-diaza-1,3-dienes 18 and/or 19 which react with dimethyl acetylenedicarboxylate (DMAD) to produce the pyrimidines 26. The 1-Boc-1,3-diaza-1,3-dienes 24 are masked forms of the 1H-dienes inasmuch as they react with DMAD under relatively mild conditions to give the dihydropyrimidine adducts 25, which are easily detectable by 1H NMR spectroscopy, and which aromatize to pyrimidines 20 at higher temperatures. The 4-methylthio compounds 31 and 33, and the 2-(trichloromethyl) compounds 37, are isolable, relatively stable, 1H-1,3-diaza-1,3-butadienes. These easily prepared compounds react with electron deficient acetylenes under mild conditions to provide the pyrimidines 20, 34, and 38, respectively, in fair to excellent yields. The 2-(trichloromethyl)pyrimidines 38 are very useful precursors of a wide variety of other 2-substituted pyrimidines 46-52.
- Guzman,Romero,Talamas,Villena,Greenhouse,Muchowski
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p. 2470 - 2483
(2007/10/03)
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- A Simple Synthesis of 2,4-Diaryl-1,3,5-triazines
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Arylamidines 2 react with 5-methoxymethylen-2,2-dimethyl-1,3-dioxan-4,6-dione 5 to give 2,4-diaryl-1,3,5-triazines in moderate to good yields. 5 can be comprehended as a formic acid derivative which transfers a C1-building block.Other formic ac
- Wessig, P.,Schwarz, J.
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- PRODUCTION OF 2,4-DISUBSTITUTED 1,3,5-TRIAZINES ON THE BASIS OF N-2,2-DICHLOROVINYLBENZIMIDOYL CHLORIDE AND ITS ANALOGS
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Treatment of the products from the condensation of N-2,2-dichlorvinylbenzimidoyl chloride and its analogs with amidines at first with chlorine and then with sodium bicarbonate leads to 2,4,6-trisubstituted derivatives of dihydro-1,3,5-triazine containing
- Popovich, T.P.,Drach, B.S.
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p. 2158 - 2164
(2007/10/02)
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- Ring Transformations and Amination in Reactions of 3-Halogeno-5-phenyl-1,2,4-triazines with Potassium Amide in Liquid Ammonia
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The reactions of 3-X-5-phenyl-1,2,4-triazines (X = fluoro, chloro, bromo, iodo) toward potassium amide/liquid ammonia were studied.Whereas the 3-fluoro compound gives only the 3-amino derivative, the 3-chloro, 3-bromo, and 3-iodo compounds yield a complex mixture containing, besides 3-amino-5-phenyl-1,2,4-triazine and 5-phenyl-1,2,4-triazine, ring transformation products, i.e., 3,5-diphenyl-1,2,4-triazine, 2,4-diphenyl-1,3,5-triazine, 6-amino-2,4-diphenyl-1,3,5-triazine, and 3-X-5-phenyl-1,2,4-triazole.Evidence is found that in the ring transformation of 3-X-5-phenyl-1,2,4-triazines into 2,4-diphenyl-1,3,5-triazines, benzamidine must be an intermediate.The mechanisms of the amination and ring transformation are extensively discussed.
- Rykowski, A.,Plas, H. C. van der
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p. 881 - 885
(2007/10/02)
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