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Method for preparing arylphosphine oxide derivatives

A technology of aryl phosphine oxide and derivatives, applied in the field of preparation of organic compounds, can solve the problems of difficult operation, harsh reaction conditions, high toxicity of reagents, etc., and achieves simple reaction operation and post-treatment process, mild reaction conditions, and reaction time. short effect

Active Publication Date: 2019-10-01
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The synthetic methods of (hetero)arylmethyl di(hetero)aryl phosphine oxides disclosed in the prior art mainly contain the following types: using substituted benzyl bromide or benzyl chloride, diaryl phosphine oxide as raw materials, under the action of strong base The following reaction obtains the corresponding product, and the method needs to use highly irritating benzyl bromide or benzyl chloride, which are very harmful to the human body and the environment; to replace benzyl alcohol or benzaldehyde, diaryl phosphorus chloride As a raw material, the corresponding product is prepared under the action of iodide ions. This method requires the use of diarylphosphine chloride. The raw material is highly toxic and easy to decompose by moisture absorption. The preparation process needs to be carried out under anhydrous conditions, and the operation is difficult; to replace benzyl alcohol and Diaryl ethoxy phosphonate is used as a raw material to prepare the corresponding product under the action of iodide ion. This method requires the use of diaryl ethoxy phosphine ester, which is difficult to obtain, easily oxidized by air, and difficult to store.
[0005] The methods disclosed above have reagents that are highly toxic, difficult to obtain, not stable enough, harsh reaction conditions, difficult to operate, and cause great harm to operators and the environment.

Method used

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  • Method for preparing arylphosphine oxide derivatives
  • Method for preparing arylphosphine oxide derivatives
  • Method for preparing arylphosphine oxide derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1: Synthesis of benzyl-diphenylphosphine oxide

[0038] Using potassium benzyl trifluoroborate and diphenyl phosphine oxide as raw materials, the reaction steps are as follows:

[0039] Add potassium benzyl trifluoroborate (99 mg, 0.5 mmol), diphenyl phosphine oxide (101 mg, 0.5 mmol), sodium persulfate (115 mg, 0.5 mmol), copper sulfate (16 mg, 0.5 mmol) into the reaction flask 0.1 mmol) and methanol (5 mL), react at room temperature;

[0040] TLC tracks the reaction until it is completely over;

[0041] After the reaction, the crude product obtained was separated by column chromatography (dichloromethane:methanol = 95:5) to obtain the target product (yield 75%). The analytical data of the product is as follows: 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.85–7.77 (m, 4H), 7.60–7.44 (m, 6H), 7.28–7.15 (m, 5H), 6.48 (dd, J = 17.8, 5.8 Hz, 1H), 5.62(t, J = 6.4 Hz, 1H).

Embodiment 2

[0042] Example 2: Synthesis of (2-chlorobenzyl)-bis(4-methoxyphenyl)phosphine oxide

[0043] Using (2-chlorobenzyl) potassium trifluoroborate and bis(4-methoxyphenyl) phosphine oxide as raw materials, the reaction steps are as follows:

[0044] Add (2-chlorobenzyl) potassium trifluoroborate (116 mg, 0.5 mmol), bis(4-methoxyphenyl) phosphine oxide (262 mg, 1 mmol), potassium persulfate (270 mg, 1.0 mmol), cuprous chloride (5 mg, 0.05 mmol) and ethanol (5 mL), 40 o C reaction;

[0045] TLC tracks the reaction until it is completely over;

[0046] After the reaction, the crude product obtained was separated by column chromatography (dichloromethane:methanol = 95:5) to obtain the target product (yield 82%). The analytical data of the product is as follows: 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.89–7.80 (m, 4H), 7.64–7.48 (m, 4H), 7.32–7.19 (m, 4H), 6.50 (dd, J = 17.8, 5.8 Hz, 1H), 5.68(t, J = 6.4 Hz, 1H), 3.67 (s, 6H).

Embodiment 3

[0047] Example 3: Synthesis of (3-chlorobenzyl)-bis(4-tolyl)phosphine oxide

[0048] Using (3-chlorobenzyl) potassium trifluoroborate and bis(4-methylphenyl)phosphine oxide as raw materials, the reaction steps are as follows:

[0049] Add (3-chlorobenzyl) potassium trifluoroborate (116 mg, 0.5 mmol), bis(4-methylphenyl) phosphine oxide (345 mg, 1.5 mmol), and ammonium persulfate (342 mg) to the reaction flask , 1.5 mmol), cuprous iodide (22.8 mg, 0.12 mmol) and acetonitrile / water (2.5 mL: 2.5 mL), 50 o C reaction;

[0050] TLC tracks the reaction until it is completely over;

[0051] After the reaction, the crude product obtained was separated by column chromatography (dichloromethane: methanol = 95:5) to obtain the target product (yield 85%). The analytical data of the product is as follows: 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.88-7.81 (m, 4H), 7.65-7.47 (m, 4H), 7.31-7.18 (m, 4H), 6.51 (dd, J = 17.8, 5.8 Hz, 1H), 5.66(t, J = 6.4 Hz, 1H), 2.21 (s, 6H).

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Abstract

The invention discloses a method for preparing aryl phosphine oxide derivatives. According to the invention, potassium (hetero) arylmethyl trifluoroborate is used as a starting material, the raw material is easy to obtain and various in types, the material is solid, and storage and use are convenient; the products obtained by the method have various types and wide applications; the derivatives canbe conveniently converted into acylphosphine acylates, and the compounds can be widely used in the production of polymer materials, coatings, adhesives, adhesive tapes and the like as photoinitiators. In addition, the method has mild reaction conditions, high yield of the target product, little pollution, simple reaction operation and post-treatment process, and is suitable for industrial production.

Description

Technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and specifically relates to a preparation method of (hetero)arylmethylbis(hetero)arylphosphine oxide derivatives. Background technique [0002] Acyl phosphonate 1 is an important compound (see document 1. Fischer M, Hickmann E, Kropp R. Preparation of α-carbonyl Phosphine oxides. U.S. Patent , 1996,5504236), its typical representative is (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (TPO, 1a) (see literature 2. Jockusch S, Koptyug I V, McGarry P F. Journal of the American Chemical Society , 1997, 119, 11495). As a photoinitiator, compound 1 is widely used in the preparation of coatings, adhesives, tapes and polymer materials (see literature 3. Nazir R, Danilevicius P, Gray D, et al. Macromolecules , 2013, 46 , 7239; 4. Benjamin D. Fairbanks, Michael P. Schwartz, Christopher N. Bowman, Kristi S. Anseth, Biomaterials 2009, 30 , 6702-6707; 5. Valter Castelvetro, Michela ...

Claims

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Application Information

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IPC IPC(8): C07F9/53C07F9/572C07F9/6553C07F9/655C07F9/58C07F9/60
CPCC07F9/5325C07F9/5337C07F9/572C07F9/655345C07F9/65515C07F9/58C07F9/60
Inventor 邹建平李成坤王松宁卞学卫
Owner SUZHOU UNIV
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