Preparation method of iron-catalyzed phosphazene compound

A technology of phosphazene and compounds, which is applied in the field of preparation of phosphazene compounds, can solve the problems of low total yield, small application range of substrates, unstable raw materials and intermediates, etc. Mild conditions and good substrate compatibility

Active Publication Date: 2019-05-17
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The method of traditional synthetic phosphazene mainly is Staudinger reaction: the reaction of phenyl azide compound and triphenylphosphine, this reaction has obtained a new compound phosphazene (azaylide or imidophosphine) quantitatively ), and release a molecule of nitrogen [see: Garcia-Alvarez, J., Garcia-Garrido, S.E., Cadierno, V.J. Wide range, but there are disadvantages such as low overall yield of multi-step reaction, unstable raw materials and intermediates
Other synthetic methods also have shortcomings such as low overall yield and small substrate scope [see: (a) Tamura Y, Minamikawa J, Haruki S, et al.Synthesis, 1974, 1974, 361. (b) Yavari I , Zabarjad-Shiraz N. Mol. Diversity, 2006, 10, 23. (c) Armstrong A, Jones L H, Knight J D, et al. Org. Lett., 2005, 7, 713. (d) Cristau H J, Hammami A, Torreilles E .Heteroat.Chem.,1999,10,49.]

Method used

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  • Preparation method of iron-catalyzed phosphazene compound
  • Preparation method of iron-catalyzed phosphazene compound
  • Preparation method of iron-catalyzed phosphazene compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1: N-(triphenyl-λ 5 -Synthesis of phosphanylidene)benzamide

[0029] Accurately weigh 3-phenyl-1,4,2-dioxazol-5-one (48.9mg, 0.3mmol), triphenylphosphine (157.2mg, 0.6mmol), ferrous chloride (1.9mg, 5mol %) into a 25mL Schlenk reaction flask, and then added toluene (2mL), placed under light conditions (1W, 280nm) and reacted at 10°C for 36h. After the reaction, the solvent was removed under reduced pressure, and petroleum ether / ethyl acetate was used as eluent, and the product was separated on a silica gel column, and the yield of the product was 95%.

[0030]

[0031] 1 H NMR (400MHz, CDCl 3 )δ8.41-8.35(m,2H),7.91-7.81(m,6H),7.59-7.53(m,3H),7.52-7.38(m,9H).

Embodiment 2

[0032] Embodiment 2: N-(triphenyl-λ 5 -Synthesis of 4-methylbenzamide

[0033] Accurately weigh 3-(4-methylphenyl)-1,4,2-dioxazol-5-one (53.1mg, 0.3mmol), triphenylphosphine (78.6mg, 0.3mmol), dinonylcarbonyl Iron (1.1 mg, 1 mol%) was added to a 25 mL Schlenk reaction flask, then dichloromethane (2 mL) was added, and the mixture was reacted at 20° C. for 24 h under light conditions (15 W, 420 nm). After the reaction was completed, the solvent was removed under reduced pressure, and petroleum ether / ethyl acetate was used as the eluent to separate on a silica gel column. The yield of the product was 91%.

[0034]

[0035] 1 H NMR (400MHz, CDCl 3 )δ8.28(d, J=8.0Hz, 2H), 7.91-7.82(m, 6H), 7.58-7.52(m, 3H), 7.51-7.43(m, 6H), 7.22(d, J=8.0Hz ,2H),2.40(s,3H).

Embodiment 3

[0036] Embodiment 3: N-(triphenyl-λ 5 -Synthesis of 3-methoxybenzamide

[0037] Accurately weigh 3-(3-methoxyphenyl)-1,4,2-dioxazol-5-one (57.9mg, 0.3mmol), triphenylphosphine (157.2mg, 0.6mmol), chloride Iron (24.3mg, 50mol%) was added into a 50mL Schlenk reaction flask, and then toluene (30mL) was added, and the mixture was reacted at 20°C for 8h under light conditions (25W, 450nm). After the reaction, the solvent was removed under reduced pressure, and petroleum ether / ethyl acetate was used as eluent, and the product was separated on a silica gel column, and the yield of the product was 90%.

[0038]

[0039] 1 H NMR (400MHz, CDCl 3 )δ8.05-8.00(m,1H),7.91-7.81(m,7H),7.59-7.53(m,3H),7.51-7.44(m,6H),7.36-7.30(m,1H),7.04- 6.98(m,1H),3.85(s,3H).

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Abstract

The invention belongs to the field of pharmaceutical and natural compound chemical intermediates and related chemical technologies, and relates to a preparation method of an iron-catalyzed phosphazenecompound. The preparation method comprises the steps that organphosphorus and 3-substituted-1,4,2-dioxazole-5-ketone serve as raw materials, cheap metal iron serves as a catalyst, and the phosphazenecompound is constructed through one step under the light condition, wherein the molar concentration of a 3-substituted-1,4,2-dioxazole-5-ketone compound in a solvent is 0.01-2 mmol/mL, and the molarratio of the 3-substituted-1,4,2-dioxazole-5-ketone compound to the adopted catalyst is (1:0.01) to (1:0.5). The preparation method has the beneficial effects that a light-catalyzed reaction is adopted, the clean and pollution-free effects are achieved, the reaction condition is mild, operation and aftertreatment are easy, and substrate compatibility is good.

Description

technical field [0001] The invention belongs to the technical field of pharmaceutical and natural compound chemical intermediates and related chemical technologies, and relates to a preparation method of an iron-catalyzed phosphazene compound. Background technique [0002] Sunlight is a prerequisite for human survival, and it is cheap, easy to obtain, clean and renewable, and is considered the most ideal energy source. Photocatalysis is a clean and non-polluting synthesis technology with mild reaction conditions. It can often avoid the use of some strong redox reagents or other toxic substances, and can largely meet people's requirements for energy and the environment. [0003] As an analogue of phosphorus ylide, phosphazene can use the lone pair of electrons on nitrogen to coordinate with transition metals. The metal complexes obtained by the coordination can be used as catalysts to catalyze many homogeneous reactions, including metal-catalyzed hydrogenation reactions, tran...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/535C07F9/655
Inventor 于晓强唐晶晶包明冯秀娟张胜
Owner DALIAN UNIV OF TECH
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