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5,10-dihydroindolo[3,2-b]indole derivative synthesis method

A technology of indoline and derivatives, applied in organic chemistry and other fields, can solve the problem of difficult preparation of substituent type diversity, etc., and achieve the effects of wide application range of substrates, easy availability of reaction raw materials, and mild reaction conditions

Inactive Publication Date: 2016-08-17
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] Since 5,10-dihydroindolo[3,2-b]indole derivatives (I) have unique photoelectric absorption activity and potential pharmacological activity, it is necessary to prepare derivatives with various types of substituents for activity research, but the current method is difficult to prepare 5,10-dihydroindo[3,2-b]indole derivatives with a variety of substituent types and easy functional group modification, and there are no reports in the literature. N'-(2,2'-(ethyne-1,2-diyl)bis(2,1-phenylene))bis(4-methylbenzenesulfonamide) derivative (II) as raw material, through acetic acid Preparation of 5,10-Dihydroindo[3,2-b]indole Derivatives by Copper-Mediated Cascade Oxidation Reaction (I)

Method used

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Embodiment 1

[0031] A synthetic method of 5,10-dihydroindo[3,2-b]indole derivatives (I), comprising the steps of:

[0032] (1) N, N'-(2,2'-(ethyne-1,2-diyl)bis(2,1-phenylene))bis(4-methylbenzenesulfonamide)(II-a) Preparation of:

[0033] Dissolve o-iodoaniline (IV-a) (220.2 mg, 1 mmol) and o-ethynyl aniline (V-a) (118.3 mg, 1 mmol) in triethylamine (50 mL), add cuprous iodide (1.9 mg , 0.01mmol), bis(triphenylphosphine)palladium dichloride (7.0mg, 0.01mmol), heated to reflux and stirred for 8h. After the reaction was detected by TLC, it was cooled to room temperature, and the solid residue was removed by vacuum filtration with a small amount of silica gel (6g). The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product 2,2'-(acetylene-1, 2-diyl)diphenylamine (III-a).

[0034] The crude 2,2'-(acetylene-1,2-diyl)diphenylamine (III-a) was dissolved in dry dichloromethane (20mL), and pyridine (1.3mL) and p-toluenesulfonyl ch...

Embodiment 2

[0038] A synthetic method of 5,10-dihydroindo[3,2-b]indole derivatives (I), comprising the steps of:

[0039] (1) N-(4-fluoro-2-((2-(4-methylphenylsulfonylamino)phenyl)ethynyl)phenyl)-4-methylbenzenesulfonamide (II-b) preparation:

[0040] Substitute (IV-a) of Example 1 with 2-iodo-4-fluoroaniline (IV-b), and others are the same as the preparation method of (III-a) in Example 1 to prepare crude product 2-((2-aminobenzene (yl)ethynyl)-4-fluoroaniline (III-b).

[0041] With reference to the preparation method of (II-a) in Example 1, prepare N-(4-fluoro-2-((2-(4-methylphenylsulfonylamino)phenyl)ethynyl)phenyl)-4 -Toluenesulfonamide (II-b): pale yellow solid, 390.8mg, yield: 73%, melting point: 189-191°C; 1 H NMR (600MHz, CDCl 3 )δ7.65(d, J=8.2Hz, 2H), 7.59(d, J=8.1Hz, 2H), 7.54(d, J=8.3Hz, 1H), 7.51(dd, J=9.0, 5.0Hz, 1H), 7.35(t, J=8.1Hz, 1H), 7.29(d, J=7.6Hz, 1H), 7.20(d, J=8.1Hz, 2H), 7.17(d, J=8.0Hz, 2H) ,7.12(t,J=7.5Hz,1H),7.07(d,J=8.6Hz,1H),7.07–7.03(m,1H),7.00(s,1H),6...

Embodiment 3

[0045] A synthetic method of 5,10-dihydroindo[3,2-b]indole derivatives (I), comprising the steps of:

[0046] (1) N-(4-chloro-2-((2-(4-methylphenylsulfonylamino)phenyl)ethynyl)phenyl)-4-methylbenzenesulfonamide (II-c) preparation:

[0047] Use 2-iodo-4-chloroaniline (IV-c) to replace (IV-a) of embodiment 1, and others are the same as the preparation method of (III-a) in embodiment 1, prepare crude product 2-((2-aminobenzene yl)ethynyl)-4-chloroaniline (III-c).

[0048] With reference to the preparation method of (II-a) in Example 1, prepare N-(4-chloro-2-((2-(4-methylphenylsulfonylamino)phenyl)ethynyl)phenyl)-4 -Toluenesulfonamide (II-c): pale yellow solid, 419.3mg, yield: 76%, melting point: 164-166°C; 1 H NMR (600MHz, CDCl 3 )δ7.65(d, J=7.7Hz, 4H), 7.57(d, J=7.9Hz, 1H), 7.53(d, J=9.1Hz, 1H), 7.38(t, J=7.8Hz, 1H) ,7.31(d,J=6.8Hz,2H),7.23(d,J=8.4Hz,5H),7.15(t,J=7.6Hz,1H),6.93(s,1H),6.85(s,1H) ,2.39(s,6H). 13 C NMR (150MHz, CDCl 3 )δ 144.5, 144.3, 137.7, 136.2, 135.9, 1...

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Abstract

The invention discloses a 5,10-dihydroindolo[3,2-b]indole derivative synthesis method. The method includes: (1) in a triethylamine solution of 2-iodoaniline derivatives (IV) and 2-acetenyl aniline derivatives (V), adding copper iodide and bis(triphenylphosphine)palladium chloride under nitrogen protection, and heating and refluxing under nitrogen protection to generate 2,2'-(acetenyl-1,2-2-yl) diphenylamine derivatives (III); (2) reacting the compounds (III), pyridines and paratoluensulfonyl chloride to generate compounds (II) at the room temperature; (3) reacting the compounds (II) and copper acetate in dimethylformamide to obtain 5,10-dihydroindolo[3,2-b]indole derivatives (I). The 5,10-dihydroindolo[3,2-b]indole derivative synthesis method has advantages of simplicity in operation, easiness in acquisition of reaction raw materials, mild reaction conditions, realization of substituent type diversity, wide substrate application range and the like.

Description

technical field [0001] The invention relates to a synthesis method of 5,10-dihydroindolo[3,2-b]indole derivatives. Background technique [0002] 5,10-Dihydroindolo[3,2-b]indole derivatives are an important class of fused ring compounds, which exist in many active natural products and material molecules, and the research on their photoelectric absorption activity has gradually attracted attention. focus on [1] . Dinaphthopyrrole[3,2-b]pyrrole [2] (A) Because of its stable structure, easy to store and not easy to decompose, it is often used as a test material for organic light-emitting diodes and organic field effect transistors. 5,10-Dihydroindo[3,2-b]indole [3] (B) As its structurally simplified analogue, it is an acene-condensed ring molecule with a pyrrolo[3,2-b]pyrrole core, which is widely used in the construction of high-spin organic polymers and organic field-effect transistor polymers . Therefore, natural products or material molecules containing such structures...

Claims

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Application Information

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IPC IPC(8): C07D487/04
CPCC07D487/04
Inventor 杜云飞于均超赵康
Owner TIANJIN UNIV
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