Synthesis method of N-heterocyclic carbene fluorescent free radical compound

A nitrogen heterocyclic carbene and synthesis method technology, which is applied in the field of synthesis of nitrogen heterocyclic carbene fluorescent free radical compounds, can solve the problems of easy removal of chlorine atoms, single free radical structure, and low photon quantum yield, so as to avoid secondary Polymerization reaction, improved stability, and good universality

Pending Publication Date: 2022-07-05
NORTHWEST UNIV(CN)
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Due to the single structure of free radicals, the development of fluorescent free radicals mainly faces the following problems: 1. The emission wavelength is generally greater than 580nm, that is, the color of fluorescence emission is mainly concentrated in orange or red light; 2. The quantum yield is generally low, and most reports The quantum yield of luminescent radicals is lower than 10%; 3. Since most of the free radicals reported so far are based on triphenylmethyl radicals substituted by polychlorine, chlorine atoms are easy to remove under light conditions, making free radicals photostable Poor sex
In view of the shortcomings of existing fluorescent free radicals such as single species, low photon quantum yield and poor photostability, it is very practical to develop a new method for preparing new fluorescent free radicals with simple synthesis, wide range of substrate application and high yield. Application meaning

Method used

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  • Synthesis method of N-heterocyclic carbene fluorescent free radical compound
  • Synthesis method of N-heterocyclic carbene fluorescent free radical compound
  • Synthesis method of N-heterocyclic carbene fluorescent free radical compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Preparation of azacyclic carbene-triphenylamine radical 1a

[0031]

[0032] Step 1: Under a nitrogen atmosphere, the Pd 2 (dba) 3 18.3 mg (0.02 mmol), 4-iodo- N , N - Diphenylaniline 371.0 mg (1.0 mmol), azacyclic carbene a 416.5 mg (1.0 mmol) and 30 mL of dioxane were added to a 100 mL Schlenk tube to obtain a brown solution. The above mixture was first stirred at room temperature for 30 min, and then the temperature was raised to 120 o C reacted for 15 h. After the reaction was completed, it was cooled to room temperature and concentrated. Add n-hexane to the Schlenk tube, stir vigorously, filter and rinse with n-hexane, and dry to obtain 747.6 mg of azacyclic carbene-triphenylamine adduct as a gray product with a yield of 95%. Elemental Analysis (%), C 47 H 54 N 3 I (761.79): C 71.18, H 6.95, N 5.81; found: C 70.95, H6.68, N 5.70. 1 H NMR (400 MHz, CD 3 CN): 0.98 (d, J = 6.8 Hz, 12H, CH(C H 3 )), 1.22 (d, J = 6.8 Hz, 12H, CH(C H 3 )...

Embodiment 2

[0035] Example 2: Preparation of azacyclic carbene-triphenylamine radical 1b

[0036]

[0037] Step 1: Under a nitrogen atmosphere, the Pd 2 (dba) 3 18.3 mg (0.02 mmol), 4-iodo-N,N-diphenylaniline 371.0 mg (1.0 mmol), azacyclocarbene b 388.5 mg (1.0 mmol) and 30 mL dioxane were added to a 100 mL Schlenk tube A brown solution was obtained. The above mixture was first stirred at room temperature for 30 min, and then the temperature was raised to 120 o C reacted for 15 h. After the reaction was completed, it was cooled to room temperature and concentrated. Add n-hexane to a Schlenk tube, stir vigorously, filter and rinse the solid with n-hexane, and dry to obtain 577.4 mg of azacyclocarbene-triphenylamine adduct as a gray product with a yield of 76%. Elemental Analysis (%), C 45 H 50 N 3 I (759.78): C 71.46, H 6.91, N 5.81; found: C 71.14, H 6.63, N 5.53. 1 H NMR (400 MHz, CD 3 CN): 1.05 (d, 3 J H,H = 6.8 Hz, 12H, CH(C H 3 )), 1.23 (d, J = 6.8 Hz, 12H, CH(C ...

Embodiment 3

[0040] Example 3: Preparation of azacyclic carbene-triphenylamine radical 1c

[0041]

[0042] Step 1: Under a nitrogen atmosphere, the Pd 2 (dba) 3 18.3 mg (0.02 mmol), 4-iodo-N,N-diphenylaniline 371.0 mg (1.0 mmol), azacyclocarbene c 390.5 mg (1.0 mmol) and 30 mL dioxane were added to a 100 mL Schlenk tube A brown solution was obtained. The above mixture was first stirred at room temperature for 30 min, and then the temperature was raised to 120 o C reacted for 15 h. After the reaction was completed, it was cooled to room temperature and concentrated. Add n-hexane to the Schlenk tube, stir vigorously, filter and rinse the filter residue with n-hexane, and dry to obtain 646.8 mg of azacyclocarbene-triphenylamine adduct as a gray product with a yield of 85%. Elemental Analysis (%), C 45 H 54 N 3 I (761.79): C 71.18, H 6.95, N 5.81; found: C 70.95, H 6.68, N 5.70. 1 H NMR (400 MHz, CD 3 CN): 1.02 (d, J = 6.8 Hz, 12H, CH(C H 3 )), 1.33 (d, J = 6.8 Hz, 12H, CH...

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Abstract

The invention discloses a synthesis method of an N-heterocyclic carbene fluorescent free radical compound, which comprises the following steps: (1) under the protection of inert gas, reacting N-heterocyclic carbene A with aryl halide B by taking Pd2 (dba) 3 or Ni (COD) 2 as a catalyst to obtain an N-heterocyclic carbene aromatic adduct C; and (2) reacting the N-heterocyclic carbene aromatic adduct C with a reducing agent KC8 to obtain the N-heterocyclic carbene fluorescent free radical compound D. Due to the introduction of N-heterocyclic carbene, the steric hindrance of the center of the free radical is increased, the dimerization reaction of the free radical can be effectively avoided, and the stability of the obtained free radical is greatly improved. And the method has the characteristics of good universality, easy product separation, high yield and the like.

Description

technical field [0001] The invention relates to a method for synthesizing a nitrogen heterocyclic carbene fluorescent radical compound, belonging to the field of synthetic chemistry. Background technique [0002] Compared with traditional closed-shell fluorescent molecules, the fluorescence emission of radical molecules with open-shell electronic structure comes from the radiation transition between doublet states, and there is no spin forbidden. Therefore, the theoretical internal quantum efficiency of OLED devices based on radical fluorescent molecules can be as high as 100% (Z. Cui, A. Abdurahman, X. Ai, F. Li, CCS Chem . 2020, 2 ,1129; L. Ji, J. Shi, J. Wei, T. Yu, W. Huang, Adv. Mater. 2020, 32 , 1908015). As early as 2006, Juliá's group reported the first carbon radical with room temperature fluorescence emission, but it did not attract researchers' research interest at that time. Until 2018, Professor Li Feng of Jilin University used free radicals as the light-e...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D233/24C07D233/02C07D235/02C07D403/10C07D233/06C07D417/04C07D409/04C07D405/04C07D403/04C07D277/04C07D209/08C07D231/56C07D249/06C07D235/18C07D239/70C09K11/06
CPCC07D233/24C07D233/02C07D235/02C07D403/10C07D233/06C07D417/04C07D409/04C07D405/04C07D403/04C07D277/04C07D209/08C07D231/56C07D249/06C07D235/18C07D239/70C09K11/06C09K2211/1029C09K2211/1044C09K2211/1059C09K2211/1037C09K2211/1088C09K2211/1092
Inventor 韩英锋李鑫
Owner NORTHWEST UNIV(CN)
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