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Synthesis method of phenoxazine compounds or phenothiazine compounds

A synthesis method and compound technology, applied in the field of oxygen and nitrogen compound synthesis, can solve the problems of narrow amine source selection range, poor functional group tolerance, harsh reaction conditions, etc., and achieve expansion tolerance, good yield, and mild reaction conditions. Effect

Inactive Publication Date: 2017-06-20
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Experimental data proves that this type of reaction has high requirements on the substrate, so the selection range is extremely narrow, and requires step-by-step reaction to close the ring, the reaction conditions are relatively harsh (such as high reaction temperature, adding a large excess of base), and the functional group tolerance is poor. , especially a narrow range of options for amine sources

Method used

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  • Synthesis method of phenoxazine compounds or phenothiazine compounds
  • Synthesis method of phenoxazine compounds or phenothiazine compounds
  • Synthesis method of phenoxazine compounds or phenothiazine compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0030] The preparation method of the phenoxazine compound A of following structural formula:

[0031]

[0032] To a dry 25 mL Schlenk reaction tube was added the dihalide compound 2,2'-dibromodiphenyl ether (0.2 mmol), followed by aniline (0.22 mmol), Pd(OAc) 2 (0.01mmol, 5mol%), DPEphos (0.02mmol, 10mol%), sodium tert-butoxide (0.6mmol), under the protection of nitrogen, add toluene (2mL), and react at 120°C for 15h. After the reaction, the target product A was obtained by extraction, drying, concentration, and column chromatography (pure petroleum ether).

[0033] 1 H NMR (600MHz, CDCl 3 ,SiMe 4 ): δ=7.53(t, J=7.74Hz, 2H), 7.41(t, J=7.38Hz, 1H), 7.29(d, J=7.86Hz, 2H), 6.66-6.65(m, 2H), 6.59 (t, J=7.68Hz, 2H), 6.54-6.52 (m, 2H), 5.87 (d, J=7.98Hz, 2H).

[0034] 13 C NMR (150MHz, CDCl 3 ,SiMe 4 ): δ=143.85, 138.90, 134.33, 130.95, 130.72, 128.38, 123.15, 121.19, 115.32, 113.16.

Embodiment 2

[0036] The preparation method of the phenoxazine compound B of following structural formula:

[0037]

[0038] Into a dry 25mL Schlenk reaction tube was added the dihalide compound 2,2’-dibromodiphenyl ether (1.2mmol), followed by p-phenylenediamine) (0.6mmol), Pd(OAc) 2 (0.06mmol, 10mol%), DPEphos (0.12mmol, 20mol%), sodium tert-butoxide (3.6mmol), under the protection of nitrogen, add toluene (2mL), and react at 120°C for 72h. After the reaction, the target product B was obtained by extraction, drying, concentration, and column chromatography (petroleum ether: ethyl acetate = 20:1, volume ratio).

Embodiment 3

[0040] The preparation method of the phenoxazine compound C of following structural formula:

[0041]

[0042] To a dry 25 mL Schlenk reaction tube was added the dihalide 2-bromo-1-(2-bromophenoxy-4-chloro)-benzene (0.2 mmol), followed by aniline (0.22 mmol), Pd(OAc) 2 (0.01mmol, 5mol%), DPEphos (0.02mmol, 10mol%), sodium tert-butoxide (0.6mmol), under the protection of nitrogen, add toluene (2mL), and react at 120°C for 15h. After the reaction, the target product C was obtained by extraction, drying, concentration, and column chromatography (pure petroleum ether).

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Abstract

The invention discloses a series of novel phenoxazine (phenothiazine) compounds and a novel synthesis method thereof. The method comprises the following steps: in a nitrogen atmosphere, dissolving bis halo compounds, primary amine, a palladium compound, a phosphine ligand and an alkali in an organic solvent, heating and stirring to react, extracting, drying, concentrating, and purifying to obtain a series of phenoxazine or phenothiazine compounds. The invention relates to the technical field of synthesis of oxygen (sulfur) nitrogen compounds, particularly a preparation method of phenoxazine (phenothiazine) compounds. The N- site bis aromatization of the bis halo compounds and primary amine is catalyzed by the palladium to synthesize the phenoxazine (phenothiazine) compounds; and thus, the method is simple to operate and easy to implement, has the advantages of simple synthesis steps, mild reaction conditions, high product yield (up to 99%) and wide substrate application range, provides a new idea for synthesis of phenoxazine (phenothiazine) compounds, and has important meanings in organic synthesis methodology.

Description

technical field [0001] The invention relates to the technical field of synthesis of oxygen (sulfur) nitrogen compounds, in particular to a class of phenoxazine and phenothiazine derivatives and a preparation method thereof. Background technique [0002] Phenoxazine and phenothiazine derivatives are a very important class of organic heterocyclic compounds, which are widely used in medicinal chemistry and In synthetic studies of biochemistry [Prinz, H.; Chamasmani, B.; Vogel, K.; et al. J. Med. Chem. 2011, 54, 4247.]. In addition, the unique electron donor structure of phenoxazine and phenothiazine makes it suitable for dye-sensitized solar cells [Lee, W.; Yuk, S.B.; Choi, J.; et al. Dyes and Pigments 2014,102,13 .], fluorescent dyes [Duan, C.; Li, J.; Han, C.; et al. Chem. Mater. 2016, 28, 5667.], and OLEDs [Okamoto, T.; Kozaki, M.; Doe , M.; etal.Chem.Mater.2005,17,5504.] and other photoelectric materials play an important role. The usual method for synthesizing phenoxazi...

Claims

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Application Information

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IPC IPC(8): C07D265/38C07D413/04C07D417/10C07D279/22C07D413/10
CPCC07D265/38C07D279/22C07D413/04C07D413/10C07D417/10
Inventor 袁冰芯张露李恒杨贯羽
Owner ZHENGZHOU UNIV
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