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Method for preparing ferrocene diphosphine ligand

A bisphosphine ligand, ferrocene technology, applied in chemical instruments and methods, metallocene, organic chemistry, etc., can solve the problems of high production equipment requirements, low reaction yield, difficult reaction control, etc., and achieve optimized separation and purification. process, ease of industrial production, changing the effect of demanding requirements

Active Publication Date: 2015-08-26
濮阳惠成新材料产业技术研究院有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, the methods for the synthesis of ferrocene bisphosphine ligands reported in the literature are generally obtained by dilithiation of ferrocene. This route is based on air-sensitive butyllithium and diarylphosphine chloride or dialkyl chloride Phosphine is used as a raw material, which makes it difficult to control the reaction in industrial production and requires high production equipment (J. Organometal. Chem., 1971, 27, 241-249; Chem. Eur. J. 2012, 18, 12267-12277)
In addition, in this method, ferrocene itself can be polymerized, resulting in a low reaction yield (60% ~ 70%), and the ferrocene polymer will also affect the catalytic activity of the generated ligand
The literature (Organometallics, 1983, 2, 714-719; J. Am. Chem. Soc., 1998, 120(29), 7369-7370) reported the synthesis method of DtBPF, but because DtBPF is easily oxidized, it is difficult to isolate Purification must be carried out under the protection of inert gas, which brings inconvenience to the operation and cannot meet the needs of industrial applications

Method used

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  • Method for preparing ferrocene diphosphine ligand

Examples

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Embodiment 1

[0015] Example 1 Synthesis of 1,1'-bis(diphenylphosphino)ferrocene

[0016] Under the protection of argon, ferrocene (1 mol, 186 g), 1 L 1,2-dichloroethane and diphenylphosphine oxide (2 mol, 405 g) were added to the dry reactor at 0 °C Add dropwise 47% mass percent boron trifluoride ether solution (5 mol, 1.52 kg) to the system under the same conditions. After the dropwise addition, raise the temperature to 60°C for 10 h, then cool down to 0°C and add water dropwise to the system for hydrolysis. Then separate the liquids, dry the organic layer with anhydrous magnesium sulfate, filter, and distill off the solvent under reduced pressure to obtain a yellow solid, which can be recrystallized from dichloromethane and n-hexane to obtain 1,1'-bis(diphenylphosphine)dicene Tetrafluoroborate of iron 686 g ( 31 P NMR (400 MHz, CDCl 3 ), δ: 4.0 ppm); add 2 L methanol to the above tetrafluoroborate, heat to reflux for 8 h, then cool and crystallize under the protection of argon, fil...

Embodiment 2

[0017] Example 2 Synthesis of 1,1'-bis(di-tert-butylphosphino)ferrocene

[0018] Under the protection of argon, ferrocene (1 mol, 186 g), 1 L of 1,2-dichloroethane and di-tert-butylphosphine oxide (4 mol, 648 g) were added to the dry reactor. At 10°C, a 47% by mass boron trifluoride ether solution (8 mol, 2.4 kg) was added dropwise to the system. After the dropwise addition, the temperature was raised to 80°C for 10 h, and then the temperature was lowered to 0°C, and water was added dropwise to the system. Hydrolyze, then separate the liquids, dry the organic layer with anhydrous magnesium sulfate, filter, and distill off the solvent under reduced pressure to obtain a yellow solid, which can be recrystallized from dichloromethane and n-hexane to obtain 1,1'-bis(di-tert-butylphosphine ) Tetrafluoroborate of ferrocene 618 g ( 31 P NMR (400 MHz, CDCl 3 ), δ: 39.9 ppm); add 2 L methanol to the above tetrafluoroborate, heat to reflux for 12 h, then cool and crystallize under ...

Embodiment 3

[0019] Example 3 Synthesis of 1,1'-bis(diisopropylphosphino)ferrocene

[0020] Under argon protection, ferrocene (1 mol, 186 g) and diisopropylphosphine oxide (4 mol, 536 g) were added to the dry reactor (according to the method of document Organometallics, 2009, 28, 6383~6401 Synthesis) and 1 L of 1,2-dichloroethane, add 47% by mass boron trifluoride ether solution (8 mol, 2.4 kg) dropwise to the system at 10°C, and raise the temperature to 70°C after the addition is complete React for 12 h, then lower the temperature to 0°C, add water dropwise to the system, hydrolyze, then separate the layers, dry the organic layer with anhydrous magnesium sulfate, filter, distill off the solvent under reduced pressure to obtain a yellow solid, recrystallize from dichloromethane and n-hexane 552 g of tetrafluoroborate of 1,1'-bis(diisopropylphosphino)ferrocene can be obtained; add 1 L of methanol to the above-mentioned tetrafluoroborate, heat and reflux for 12 h, and then protect with a...

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Abstract

The invention discloses a method for preparing ferrocene diphosphine ligand, and belongs to the field of organic synthesis. The method comprises the following steps: by taking ferrocene as an initial raw material and boron trifluoride diethyl etherate as a catalyst, reacting with diaryl phosphine oxide or dialkyl phosphine oxide, hydrolyzing so as to obtain tertfluoborate of a ferrocene diphosphine compound, and performing heating backflow deprotection in methanol, thereby obtaining the ferrocene diphosphine compound. Compared with the prior art, the method is gentle in reaction condition, simple in aftertreatment, and relatively applicable to industrial production, and the yield is greater than 90%. The prepared ferrocene diphosphine can be used as ligand of a metal catalyst, and can be used in the fields such as organic optoelectronic materials and medicines.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a synthesis method of a class of organic phosphine compounds, in particular to a synthesis method of ferrocene bisphosphine compounds. Background technique [0002] As a class of important intermediates and catalyst ligands, ferrocene bisphosphine compounds are widely used in the synthesis of natural products, drugs, functional materials, liquid crystal molecules and biologically active compounds. The unique electronic effect and steric structure of the ferrocene skeleton make the ferrocene-based phosphine ligands exhibit good activity when applied to catalytic coupling reactions. For example, 1,1'-bis(diphenylphosphino)ferrocene (DPPF) can be used as an effective catalyst for the construction of C-C / C-N / C-O bonds in organic synthesis after complexation with transition metals, 1,1'-bis( Di-tert-butylphosphino)ferrocene (DtBPF) has better activity in activating carbon-chlorine bond...

Claims

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Application Information

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IPC IPC(8): C07F17/02
CPCC07F17/02
Inventor 陈辉杨瑞娜杨振强张银龙周铎孙敏青屈凤波
Owner 濮阳惠成新材料产业技术研究院有限公司
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