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Method for synthesizing 1,2-bibenzyl compound

A technology for diarylethane and compounds, which is applied in the field of synthesizing 1,2-diarylethane compounds, can solve the problems of unfavorable large-scale industrial application, narrow substrate applicability, and high price, so as to avoid external compounding The use of body, good catalytic activity, low price effect

Active Publication Date: 2018-05-08
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, transition metal-catalyzed cross-coupling reactions between benzoheteroarenes and styrene compounds have attracted people’s attention and become a new method for the synthesis of 1,2-diarylethane compounds; however, existing There are obvious limitations in the method, such as the use of noble metal iridium catalysts, or the use of zero-valent nickel (0) catalyst Ni(COD) which is very sensitive to oxygen and moisture and has a high price. 2 , the latter catalyst also needs to use very sensitive and dangerous trimethylaluminum at the same time, which is extremely flammable when exposed to air, and will explode when it meets water; in addition, the applicability of the existing method substrate is very narrow, These are not conducive to large-scale industrial application

Method used

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  • Method for synthesizing 1,2-bibenzyl compound
  • Method for synthesizing 1,2-bibenzyl compound
  • Method for synthesizing 1,2-bibenzyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Example 1 Ni[P(OEt) 3 ][(RNCHCHNR)C]Br 2 Synthesis

[0041] Nitrogen heterocyclic carbene (RNCHCHNR) C (0.9470 g, 1.0 mmol) was added to a tetrahydrofuran solution of bis(triethylphosphite) nickel(II) bromide (0.5500 g, 1.0 mmol), and reacted at 60°C Overnight, the solvent was removed in vacuo, the residue was washed with n-hexane, the obtained residue was extracted with tetrahydrofuran, the clear liquid was transferred and the solvent tetrahydrofuran was removed to obtain a red solid as a divalent nickel (II) complex with a yield of 60%.

[0042] The product was subjected to elemental analysis, and the results are shown in Table 1:

[0043] Table 1 Elemental analysis results

[0044]

C：（%）

H：（%）

N：（%）

theoretical value

67.69

5.45

2.10

actual value

67.87

5.61

2.06

[0045] The product was characterized by NMR, and the results are as follows:

[0046] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal t...

Embodiment 2

[0051] Example 2 The divalent nickel (II) complex is used as a catalyst to catalyze the cross-coupling reaction of benzoheteroarenes and styrene compounds

[0052] Under argon protection, catalyst (66 mg, 0.05 mmol, 10 mol%), magnesium chips (12.0 mg, 0.5 mmol), benzothiazole (54 μl, 0.5 mmol), benzene Ethylene (86 microliters, 0.75 mmol), tetrahydrofuran (1.5 milliliters) were used as solvents, reacted at 80 °C for 60 hours, terminated the reaction with water, extracted the reaction product with ethyl acetate, and purified it by column chromatography (using ethyl acetate / petroleum A mixed solvent with a volume ratio of ether of 1:20 was used as a developer), and the yield was 90%.

[0053] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature:1 H NMR (400 MHz, CDCl 3 ) δ 7.99 (d, J = 8.1 Hz, 1H), 7.81 (d, J = 7.9 Hz,1H), 7.51 – 7.39 (m, 1H), 7.39 – 7.15 (m, 6H), 4.27 – 3.30 (...

Embodiment 3

[0054] Example 3 The divalent nickel (II) complex is used as a catalyst to catalyze the cross-coupling reaction of benzoheteroarenes and styrene compounds

[0055] Under the protection of argon, the catalyst (66 mg, 0.05 mmol, 10 mol%), magnesium chips (12.0 mg, 0.5 mmol), benzoxazole (51 μl, 0.5 mmol), and Styrene (86 microliters, 0.75 mmol), tetrahydrofuran (1.5 milliliters) were used as solvents, reacted at 90 °C for 36 hours, and terminated the reaction with water. The reaction product was extracted with ethyl acetate and purified by column chromatography (with ethyl acetate / A mixed solvent with a volume ratio of petroleum ether of 1:20 was used as a developer), and the yield was 89%.

[0056] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 7.63−7.55 (m, 1H), 7.43−7.34 (m, 1H), 7.26−7.09 (m, 7H), 3.14 (s, 4H).

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Abstract

The invention discloses a method for synthesizing a 1,2-bibenzyl compound. According to the method, a nickelous (II) complex with the molecular formula being Ni[P(OEt)3][(RNCHCHNR)C]Br2 serves as a catalyst, wherein R is 2,6-diphenyl methyl-4-methoxyphenyl), and in the presence of metal magnesium, the 1,2-bibenzyl compound is synthesized through a cross-coupling reaction of benzo-(hetero)arene anda styrene compound. According to the method, the nickelous (II) complex with air stability serves as the catalyst for the first time, so that direct use of sensitive and dangerous metal compounds andzero-valent nickel (0) complexes is avoided; under mild reaction conditions, a zero-valent nickel (0) active center is formed in situ through the action of the metal magnesium, so that the cross-coupling reaction between the benzo-(hetero)arene and the styrene compound is achieved, and a novel method is provide for synthesis of the 1,2-bibenzyl compound.

Description

technical field [0001] The invention belongs to organic synthesis reaction, in particular to a method for synthesizing 1,2-diarylethane compounds. Background technique [0002] As important structural units, 1,2-diarylethane compounds widely exist in drug molecules and bioactive molecules (see: Giorgioni, G.; Accorroni, B.; Di Stefano, G.; Marucci, A. ;Siniscalchi, A.; Claudi, F.; Med Chem Res 2005, 14 , 57). In recent years, transition metal-catalyzed cross-coupling reactions between benzoheteroarenes and styrene compounds have attracted people’s attention and become a new method for the synthesis of 1,2-diarylethane compounds; however, existing There are obvious limitations in the method, such as the use of noble metal iridium catalysts, or the use of zero-valent nickel (0) catalyst Ni(COD) which is very sensitive to oxygen and moisture and has a high price. 2 , the latter catalyst also needs to use very sensitive and dangerous trimethylaluminum at the same time, which...

Claims

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Application Information

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IPC IPC(8): C07B37/00C07D235/08C07D263/56C07D277/64C07F15/04B01J31/22
CPCB01J31/185B01J31/2273B01J2231/4205B01J2531/847C07B37/00C07D235/08C07D263/56C07D277/64C07F15/04
Inventor 孙宏枚李瑞鹏
Owner SUZHOU UNIV
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