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Benzocyclobutadienopyrrole derivatives with aee effect and their preparation

A technology for benzocyclobutadiene and pyrrole derivatives, which is applied in the field of organic synthesis, can solve problems such as limitation, and achieves the effects of cheap and easy-to-obtain raw materials and simple operation.

Inactive Publication Date: 2019-06-28
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Throughout the reported AIE / AEE compounds, most of them are derivatives based on silole (silole) or tetraphenylethylene (Tetraphenylethene, TPE) as the main core structure, indicating that the core structure compounds with AIE / AEE properties are relatively limited
In addition, the emission wavelength of fluorescent compounds with TPE or Silole as the core is mainly limited to the blue or yellow light region, and the background fluorescence of some AIE dyes in the blue and yellow light region will limit its application.

Method used

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  • Benzocyclobutadienopyrrole derivatives with aee effect and their preparation
  • Benzocyclobutadienopyrrole derivatives with aee effect and their preparation
  • Benzocyclobutadienopyrrole derivatives with aee effect and their preparation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] (1) Preparation of 1-p-benzoic acid ethyl-2,5-diphenyl-3,4-diiodopyrrole

[0046] (1.1) Add 1.2-diphenylethyne (2.0104g, 10.04mmol), ethyl p-aminobenzoate (6.6340g, 40.16mmol) and CuCl (0.0983g, 1.004mmol) into a 100mL polymerization tube, and vacuum Pass nitrogen three times; then, under the protection of nitrogen, first activate at 110°C for 30min, and then react at 140°C for 24h; Suction filtration after drying over anhydrous magnesium sulfate, spinning to obtain the crude product; use gel chromatography (dichloromethane:petroleum ether=1:2) to purify the crude product to obtain 2.0028g of white flocculent product, which is 1-Ethyl-p-benzoate-2,5-phenylpyrrole;

[0047] (1.2) 1-p-benzoic acid ethyl-2,5-phenylpyrrole (1.4846g, 3.90mmol), ICl (2.0082g, 12.83mmol) and NaHCO 3 (0.8668g, 10.56mmol) is added in the two-necked flask of 100mL, under nitrogen protection, add 30mL diethyl ether and react 24h under nitrogen protection; 5% hydrochloric acid aqueous solution w...

Embodiment 2

[0057] The 4-ethynyltoluene used in step (2) of Example 1 is replaced by 2-(4-phenylethynyl ether)-1,3-dioxolane with a molar number of 2 mmol, and other steps and parameters are the same as in Example 1 Same, that is, benzocyclobutadienopyrrole derivatives are obtained.

[0058] The product prepared in this implementation is characterized, and the data of its proton nuclear magnetic spectrum and mass spectrum are as follows:

[0059] 1 H NMR (400MHz, CDCl 3 )δ7.74(dd, J=8.3,6.6Hz,2H),7.66(d,J=8.2Hz,1H),7.51(d,J=8.0Hz,2H),7.44(d,J=8.2Hz, 1H),7.25–7.20(m,1H),7.19(d,J=3.4Hz,3H),7.17–7.10(m,3H),7.08(d,J=6.6Hz,1H),7.03(dd,J =13.1,5.4Hz,2H),6.87(ddd,J=21.0,13.9,7.8Hz,6H),6.77(t,J=7.2Hz,2H),6.62(dd,J=17.7,9.9Hz,2H) ,6.46(d,J=7.3Hz,1H),5.85(d,J=17.0Hz,1H),5.77–5.70(m,1H),5.62(s,1H),4.30(qd,J=7.1,3.4 Hz, 2H), 4.18–3.95(m, 12H), 1.33(td, J=7.1, 3.1Hz, 3H;

[0060] MS (ESI + ):Molecular formula C 58 h 48 o 8 N, m / z: calculated value [M+H] + =886.3374, test value [M+H] + =886...

Embodiment 3

[0065] The 4-ethynyltoluene used in the step (2) of Example 1 was replaced by phenylacetylene of an equimolar number, and the reaction at 100°C for 24h in the step (2) of Example 1 was replaced by the reaction at 60°C for 15h, The other steps and parameters were the same as in Example 1 to obtain benzocyclobutadienopyrrole derivatives.

[0066] The product prepared in this implementation is characterized, and the data of its proton nuclear magnetic spectrum and mass spectrum are as follows:

[0067] 1 H NMR (400MHz, CDCl 3 )δ7.79–7.64(m,3H),7.50(dd,J=20.7,7.5Hz,1H),7.43–7.29(m,3H),7.22–6.44(m,23H),4.30(q,J= 7.0Hz, 2H), 1.34(t, J=7.1Hz, 3H);

[0068] MS(MALDI-TOF): Molecular Formula C 49 h 35 NO 2 , m / z: calculated value [M] = 669.2668, test value [M] = 669.2685;

[0069] According to the characterization results of proton nuclear magnetic spectrum and mass spectrum, the structural formula of the benzocyclobutadienopyrrole derivative prepared in this embodiment is as fol...

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Abstract

The invention relates to a cyclobutadiene benzopyrrole derivative with an AEE effect and preparation thereof and belongs to the technical field of organic synthesis. The cyclobutadiene benzopyrrole derivative is a benzo condensed ring derivative with pyrrole-cyclobutadiene-benzene ring combined in a large pi conjugated structure, and has an AEE property; the light-emitting wavelengths are higher than 550nm, the light is located in an orange light region or a red light region, and the derivative can be used for synthesizing an infrared or far infrared organic fluorescent dye. The method of preparing the cyclobutadiene benzopyrrole derivative is a one-pot method which mainly comprises the steps of performing continuous Sonogashira reaction and cyclotrimerization reaction on a pyrrole derivative iodated in sites 3 and 4 to form an aromatic pi system with a five membered ring combined with a four membered ring and a six membered ring. The method is simple to operate and the used raw materials are cheap and easily available.

Description

technical field [0001] The invention relates to a fluorescent compound, in particular to a benzocyclobutadienopyrrole derivative with AEE effect and its preparation, belonging to the technical field of organic synthesis. Background technique [0002] As early as 1881, researchers discovered fluorescent compounds. For more than a hundred years, fluorescent compounds have been used in various fields, such as light-emitting diodes, biological probes, and chemical sensing. Organic fluorescent dyes have unique advantages in chemical detection and biological applications due to their modifiable organic groups and low toxicity to organisms. However, traditional organic fluorescent dyes have good luminescence in dilute solutions, but their luminescence intensity gradually decreases with the increase of the concentration in the solution. This phenomenon is called Aggregation-Caused Quenching (ACQ) . The ACQ phenomenon exists because the fluorescent compounds are mostly aromatic str...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D209/94C07D405/14C09K11/06
CPCC07D209/94C07D405/14C09K11/06C09K2211/1029C09K2211/1088
Inventor 石建兵任飞董宇平佟斌支俊格罗姗姗刘国罡
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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