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Pinene condensed chiral terpyridyl bidentate compound and preparation method thereof

A technology for terpyridine and compound, which is applied in the field of synthesis and preparation of bidentate compounds, can solve the problems of few reports and researches on tridentate ligands, and achieves the effects of good coordination ability, simple operation, and cheap and easy-to-obtain raw materials.

Inactive Publication Date: 2019-12-31
ZHENGZHOU UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although there are many reports on various tridentate organoplatinum compounds, there are few reports on the tridentate ligands of imidazolines, so the synthesis of this type of compounds has certain practical and theoretical significance.

Method used

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  • Pinene condensed chiral terpyridyl bidentate compound and preparation method thereof
  • Pinene condensed chiral terpyridyl bidentate compound and preparation method thereof
  • Pinene condensed chiral terpyridyl bidentate compound and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0020] The preparation method of the pinene-fused chiral terpyridine bidentate ligand compound of this embodiment is as follows:

[0021] Under the protection of inert gas, into a 50mL Shrek bottle, add compound 11 (150mg, 0.3mmol), chiral terpyridine 7 (450mg, 0.9mmol), Pd(PPh 3 ) 4 (35mg, 0.03mmol), Na 2 CO 3 (320mg, 3mmol), toluene (10mL), tert-butanol (4mL) and deionized water (4mL), flush three times and seal. The reaction was placed in an oil bath and reacted at 80°C for 48h. After the reaction was completed, cool to room temperature, dissolve the solid with dichloromethane, and wash the organic phase with 50 mL of deionized water. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent was removed in vacuo. Afterwards, the crude product was purified by column chromatography (eluent: dichloromethane, dichloromethane / methanol=100:0.6) and further purified by column chromatography (eluent: chloroform) to obtain 140 mg of a brown-yellow so...

Embodiment 2

[0024] The synthetic route of chiral terpyridine 7 is as follows:

[0025]

[0026] Synthesis of compound 1

[0027] Install a reflux tube, a drying tube and a hollow plug on a 1000mL three-neck round bottom flask, and install a calcium chloride drying tube on the upper end of the reflux tube. Weigh metallic sodium (13.8g, 0.6mol) and cut it into small pieces, and add it into a three-necked flask containing absolute ethanol (300mL, 5mol) in six to seven times. After the metal sodium and ethanol react completely and cool to room temperature, replace the reflux tube with a constant pressure dropping funnel. At room temperature, a mixed solution of anhydrous acetone (22.8mL, 0.3mol) and diethyl oxalate (86.4mL, 0.6mol) was added dropwise to sodium ethoxide / ethanol, a yellow precipitate formed during the dropwise addition. When remaining 1 / 4, transfer to 60°C oil bath until the dropwise addition is complete. During this process, the aforementioned yellow solid dissolved and ...

Embodiment 3

[0056] Boric acid pinacol ester compound 11 is 9-hexyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) The synthetic route of -9H-carbazole is as follows:

[0057]

[0058] Synthesis of compound 9

[0059] Compound 8 (3.30 g, 20 mmol) and KOH (2.96 g, 52.8 mmol) were dissolved in DMF (40 mL) and stirred for 60 min at room temperature. Then, add n-C dropwise 6 h 13 Br (3.30 g, 20 mmol), and the reaction mixture was stirred at room temperature for 48 h. Afterwards, the mixture was poured into deionized water and extracted with chloroform, and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was purified by silica gel column chromatography with n-hexane to obtain compound 9 with a yield of 90.9%. The product is a known compound, the 1 H NMR confirmed.

[0060] 9-hexyl-9H-carbazole (9)

[0061]Yellow solid; Mp 61-62℃;

[0062] 1 H NMR (400MHz, CDCl 3 )(δ,ppm)8.10(d,J=...

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Abstract

The invention discloses a pinene condensed chiral terpyridyl bidentate compound and a preparation method thereof. The compound has a structure formula shown in the description. Commercial diethyl oxalate and acetone are adopted as initial raw materials, the initial raw materials are subjected to a Suzuki coupling reaction with a boronic acid pinacol ester compound, and thus a chirally modified terpyridyl bidentate ligand is synthesized. The synthesis method disclosed by the invention is simple in operation, and the raw materials are low in price and easy to obtain. A terpyridyl compound can beused as the tridentate ligand to form a stable complex together with multiple transition metals and rare earth metal ions, and in addition, the complex has good catalysis performance and special redox, photophysical properties, and the like, and can be applied to fields such as material science, life science, supramolecular self assembling, molecular catalysis and DNA (deoxyribonucleic acid) chips.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of organic compounds, and in particular relates to the synthesis and preparation method of a pinene-fused chiral terpyridine bidentate compound. Background technique [0002] In 1932, Morgan and Burstal first reported the synthesis of terpyridine (J.Chem.Soc., 1932, 20.), because terpyridine and its structural analogues have good coordination ability and are easy to form stable coordination with ions. Compounds (Angew.Chem., Int.Ed., 2002, 41, 2892-2926; Chem.Soc.Rev., 2004, 33, 373-399; Chem.Soc.Rev., 2011, 40, 1459-1511.) , is a widely used ligand in modern coordination chemistry. [0003] Since 2,2':6',2"-terpyridine contains three nitrogen atoms, it can be used as a tridentate ligand to form stable complexes with various transition metal and rare earth metal ions, and the complexes have Good catalytic performance and special redox, photophysical properties, etc., and applie...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D401/14
CPCC07D401/14
Inventor 邵田刘爽谢晓娜屈菁菁赵福杰姜辉朱新举郝新奇
Owner ZHENGZHOU UNIV
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