2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶的合成及其光谱性能

以咔唑和2,5-二溴吡啶为初始原料,经Ullmann反应、NBS亲电取代反应和Suzuki偶联等反应,合成了一种新型的磷光配体2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶(5),其结构经1HNMR,ESI-MS及元素分析表征。研究了5在二氯甲烷中的荧光光谱和紫外吸收光谱。     

Access to polycyclic carbazoles from ring-fused 2-(9H-carbazol-1-yl)anilines

Abstract

Nine 2-(9H-carbazol-1-yl)anilines with rings fused at the 3,4-position were acylated at the amino group with chloroacetyl, 3-chloropropanoyl, or 4-chlorobutyryl chloride, at yields of 85–99%. The resulting ω-chloroamides were exposed to potassium tert-butoxide in THF. All nine acetamides annulated exclusively at the carbazole N atom, giving benzodiazocinocarbazoles at 76–91% overall yield. The only propanamide prepared underwent α,β-elimination, giving the corresponding acrylamide at 70% overall yield. All nine butanamides annulated exclusively at the amide nitrogen, giving pyrrolidin-2-ones at 70–94% overall yield. Additionally, the 1-indanone derived carbazolylaniline followed the same annulation pattern, but the benzylic methylene group was oxidized, giving the corresponding fluorenones. The cyclohexanone-derived carbazolylaniline was also converted into a maleimide, which participated in a Diels-Alder reaction with cyclopentadiene. Attempts to replace the amino group in the starting material via diazotization were unsuccessful. Instead, a Widman-Stoermer reaction was observed, in which the diazonium group attacked the carbazole 2-position, giving the corresponding cinnoline.     

Synthesis of Derivatives of 1-(9-Alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones

Derivatives of 1-(9-alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones (methyl esters, hydrazides) were synthesized. The condensation of the synthesized hydrazides with aromatic aldehydes, acetylacetone, and acetoacetic ester was studied. Structure of the obtained compounds was confirmed by IR and NMR spectroscopy. The specific characteristics of the substituents are discussed.     

N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺的合成

以3,5-二溴苯胺,碘苯和咔唑为原料,经取代和Ullmann反应合成了一个新的含咔唑三苯胺化合物——N,N-二[4-(9H-9-咔唑基)苯基]-3,5-二溴苯胺,其结构经1H NMR,13C NMR和ESI-MS表征。     

A facile synthesis of novel benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones

A facile synthesis of hitherto unreported benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones (3a?Cl) is described. The synthesis mainly relies on the ultrasound-assisted Rap?CStoermer reaction of 3-chloroacetyl-9-methyl-9H-carbazole (1) with a variety of salicylaldehydes, as well as 2-hydroxy-1-naphthaldehyde (2) in CH₃CN, with the presence of PEG-400 as a catalyst. This procedure offers easy access to benzofuran-2-yl(carbazolyl)methanone derivatives in a short reaction time and the products are achieved in good yields.     

Mild synthesis of 5-(9-ethyl-9H-carbazol-3-yl)-N-aryl-1,3,4-thiadiazol-2-amines

An efficient synthetic method for heterocycles containing both carbazole and 1,3,4-thiadiazole moieties is described. 9-Ethyl-9H-carbazol-3-carbaldehyde reacted with 4-arylthiosemicarbazides, with acetic acid as catalyst, to give 1-(9-ethyl-9H-carbazol-3-yl)methylene-4-arylthiosemicarbazides, which were further treated with manganese dioxide at room temperature in acetone to give 5-(9-ethyl-9H-carbazol-3-yl)-N-aryl-1,3,4-thiadiazol-2-amines in good to high yield. This procedure has the advantages of mild conditions, easy separation, and simple manipulation.     

基于N-乙基咔唑-2-乙烯基-8-羟基喹啉锌的黄绿色有机电致发光器件的性能

通过用一种既具有空穴传输特性又具有发光特性的新型荧光染料N-乙基咔唑-2-乙烯基-8-羟基喹啉锌((E)-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl) quinolato-zinc, CzHQZn)作为受主, 制备了结构为ITO/2T-NATA (30 nm)/CBP: 6%Ir(ppy)3:wCzHQZn(20 nm)/Alq3(50 nm)/LiF/Al(ITO: indium-tin oxide, 2T-NATA: 4,4',4'-{N,N-(2-naphthyl)-N-phenylamino}-triphenylamine, CBP: 4,4-N,N'-dicarbazole-biphenyl, Ir(ppy)3: factris (2-phenylpyridine) iridium, Alq3: tris(8-quinolinolato) aluminum; w 是CzHQZn 的质量分数)的黄绿色有机电致发光器件(OLEDs). 研究了掺杂体系在不同掺杂浓度(w=5%、10%、12%、15%)时的电致发光(EL)特性. 结果表明, CzHQZn 掺杂浓度为10%的器件在11 V 电压下实现了黄绿光发射, 色坐标为(0.4045, 0.5113), 最大发光亮度为16110 cd·m-2; 而在7 V电压下的最大发光效率为2.19 cd·A-1, 最大外量子效率为0.775%.     

Synthesis, Crystal Structure and Theoretical Studies of (E)-1-((9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl)methylene)thiosemicarbazide

A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769(5), b = 8.279(5), c = 17.166(5) , β = 114.391(5)°, V = 1911.6(14) 3, Z = 4, F(000) = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ > 2σ(Ⅰ). The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory (TD-DFT) at the B3LYP/6-31G (d) level.     

Synthesis,characterization, and biological activity of a Cu(I) complex with 2-(9H-carbazol-9-yl) acetic acid

A new dicopper(I) complex with 2-(9H-carbazol-9-yl) acetic acid (HL) of the formula [Cu₂(dppm)₂L(NO₃)(CH₃OH)] [dppm = bis(diphenylphosphino)methane] was prepared. The complex was structurally characterized by IR, ¹H NMR spectra, and elemental analysis. Single crystal X-ray crystallography revealed that this complex is monoclinic, space group P2₁/c, with a = 13.6552(17) Å, b = 23.123(2) Å, c = 19.257(2) Å, α = γ = 90.00°, β = 106.860(2)°, V = 5818.8(11) ų, Z = 4, D _Calcd = 1.386 mg m^?3, F(000) = 2512, goodness-of-fit = 1.015. The complex was also tested in vitro for its cytotoxic activity using human hepatocellular carcinoma cell line (BEL-7402) and human hepatocellular liver carcinoma cell line (Hep-G2); 5-Fluorouracil was used as a positive control substance. The results indicated that the complex exhibited good cytotoxic activity against both human tumor cell lines.     

Synthesis and Crystal Structure of {4-[2-（9- Hexyl-9H-carbazol-3-yl）vinyl]phenyl} Dimethylamine

The title compound {4-[2-(9-hexyl-9H-carbazol-3-yl)vinyl]phenyl} dimethylamine has been synthesized by the well known Wittig reaction, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 47.87(2), b = 10.222(4), c = 9.612(4) , β = 92.401(9)o, V = 4699(3) 3, Z = 8, C28H32N2, Mr = 396.56, Dc = 1.121 g/cm3, F(000) = 1712 and μ(MoKa) = 0.065 mm-1. The final R and wR are 0.0793 and 0.1983, respectively for 3524 observed reflections with I > 2σ(I). In the title compound, the bond lengths are normal, and the crystal is stabilized by Van der Waals’ forces.     

Unraveling solvent-dependent hydrogen bonding interaction and excited-state intramolecular proton transfer behavior for 2-(benzo[d]thiazol-2-yl)-4-(9H-carbazol-9-yl)phenol: A theoretical study

Organic chemosensors with excited-state intramolecular proton transfer (ESIPT) behavior have attracted much attention because it has great potential in a wide range of applications. Considering the paramount behavior of excited-state relaxation, in this work, we mainly focus on deciphering photo-induced hydrogen bonding effects and ESIPT mechanism for the novel 2-(benzo[d]thiazol-2-yl)-4-(9H-carbazol-9-yl)phenol (mCzOH) dye. Considering the effects of different solvents on excited-state dynamics of mCzOH flurophore, we adopt four solvents with different polarities. Analyses of fundamental structural changes, infrared (IR) vibrational spectra, and core valence partition index between S₀ and S₁ state, we confirm hydrogen bond O H···N of mCzOH should be enhanced via photoexcitation. Especially, the increase of solvent polarity could promote hydrogen bonding strengthening degree. Intramolecular charge transfer (ICT) resulting from photoexcitation qualitatively facilitates the ESIPT occurrence to a large extent. For further checking and probing into ESIPT mechanism, via constructing potential energy curves (PECs) in four solvents, we clarify the ESIPT behavior for mCzOH. Most worthy of mention is that polar solvent plays critical roles in lowering potential barrier of ESIPT reaction and in facilitating ESIPT process. We not only clarify the detailed excited-state process, but also present the solvent-polarity-dependent ESIPT mechanism for mCzOH fluorophore.     

双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1H)-酮的合成与性能研究

设计并合成了一种基于喹诺酮衍生物的双极绿色磷光主体材料1-甲基-3-[4-(9-咔唑基)苯基]-4-苯基喹啉-2(1 H)-酮.计算发现,化合物的HOMO轨道的电子云位于咔唑基团,LUMO轨道的电子云位于喹诺酮基团,是一种良好的双极材料.化合物的磷光发射峰为515 nm(2.41 eV),符合绿色磷光主体材料的基本要求(>2.4 eV).热失重和差热分析结果表明,该化合物具有较高的热稳定性,分解温度和玻璃化转变温度分别为312℃和105℃.研究结果表明:该新型化合物是一种潜在的具有双极特性的绿色磷光主体材料.     

Synthesis and spectroscopic characterisation of (E)-2-(2-(9-(4-(1H-1,2,4-triazol-1-yl)butyl)-9H-carbazol-3-yl)vinyl)-3-ethylbenzo[d]thiazol-3-ium, a new ligand and potential DNA intercalator

Three new compounds based on carbazole planar skeleton were synthesised. Among them there is a new ligand and a potential DNA intercalator which contains a benzothiazolium moiety connected to the carbazole ring by a vinyl bridge. The absorption and emission spectral properties of this new ligand have been studied by spectroscopic methods.     

4-Aryl-5-(pyrimidin-2′-yl)-1,4-dihydropyridines,-1,4-di- and -1,2,3,4-tetrahydropyrimidines

2-Acetonylpyrimidines readily undergo the Hantzsch—Biginelli cyclocondensation. This method was used to obtain derivatives of 1,4-dihydropyridine and 1,4-di- and 1,2,3,4-tetrahydropyrirrzidines, containing the pyrimidine fragment in the 5 position of the heterocycle.Institute of Bioorganic Chemistry and Petroleum Chemistry, Ukrainian Academy of Sciences, Kiev 253660. Translated from Khimiya Geterotsiklcheskikh Soedinenii, No. 5, pp. 679–685, May, 1994. Original article submitted January 20, 1994.     

Facile Synthesis of Some 3-(Benzimidazol-2-yl)- and 3,6-Di(Benzimidazol-2-yl)-9-ethyl-9H-carbazoles

A simple and efficient synthesis of novel 3-(benzimidazol-2-yl)- and 3,6-di(benzimidazol-2-yl)-9-ethyl-9H-carbazoles is described. The synthetic approach for the preparation of 2-substituted benzimidazoles 4–8 and bis-benzimidazoles 9–12 was achieved by the condensation of carbazole-3-carbaldehyde 2 and carbazole-3,6-dicarbaldehyde 3 with o-phenyldiamines in dimethylformamide or dimethylsulfoxide in moderate to excellent yield. The identities of synthesized compounds were confirmed using ¹H NMR, ¹³C NMR, infrared (IR), and high-resolution mass spectrometry (HRMS).     

Synthesis and molecular structure of 3-[5-(quinolin-2-yl)penta-1,4-dien-1-yl]-1,4-benzodioxin-2-one

Acid-catalyzed reaction of 6,10a-dihydroxy-3,4a,7,9-tetra(tert-butyl)-1,2,4a,10a-tetrahydrodibenzo-[b,e][1,4]dioxine-1,2-dione with 4-chloro-2,7,8-trimethylquinoline gave previously unknown 3,6,8-tri-tert-butyl-3-[2-tert-butyl-5-(4-chloro-7,8-dimethylquinolin-2-yl)-4-hydroxy-3-oxopenta-1,4-dien-1-yl]-5-hydroxy-1,4-benzodioxin-2-one whose structure was determined by X-ray analysis. The energy and structure parameters of possible isomers of the product in the gas phase and in solution were estimated by PBE0/6-31G** quantum-chemical calculations.     

Synthesis of σ-(o-carboran-9-yl)- and σ-(m-carboran-9-yl)-π-cyclopentadienyldicarbonyliron and their rearrangement in reactions with bromine to π-(o-carboran-9-yl)cyclopentadienyl- and π-(m-carboran-9-yl)cyclopentadienyl-dicarbonylironbromides,respectively

9-o- and 9-m-carboranylcarboxylic acids were used to synthesize σ-(o-carboran-9-yl)- and σ-(m-carboran-9-yl)-π-cyclopentadienyldicarbonyliron. The latter complexes, in reactions with bromine, undergo rearrangement with the cleavage of the BFe σ-bond, involving migration of the 9-o- and 9-m-carboranyl groups into the cyclopentadienyl ring, to give π-(o-carboran-9-yl)cyclopentadienyl- and π-(m-carboran-9-yl)cyclopentadienyl-dicarbonyliron bromides, respectively. A simple method to obtain these acids by the oxidation of 9-alkyl-o- and 9-alkyl-m-carboranes with CrO₃ in CH₃COOH has been found.