Synthetic method of trisubstituted oxaphosphinane compound or trisubstituted dioxaphosphinane compound

Abstract

The invention provides a synthesis method of a trisubstituted phosphine oxide compound or a trisubstituted phosphine oxide compound. The method uses cheap, easy-to-obtain, wide-sourced, stable and low-toxic alcohols or diols as alkylating agents, uses cheap and easily-available iodine salts as catalysts, and directly obtains trisubstituted phosphine oxides or dioxanes through selective reactions without solvents. Phosphine compounds. The reaction method is simple, the conditions are mild, no solvent is needed, and the operation is easy. The method has lower requirements on reaction conditions, can use benzyl type, allyl type and aliphatic alcohols as alkylating reagents, can realize the synthesis of target phosphine oxide compounds, and has a wide application range. This method can also be easily scaled up to 20 times for production, and the gram-level preparation of the product should be carried out, so it should also have certain research and industrial application prospects.

Description

technical field [0001] The present invention belongs to the field of chemical synthesis, specifically refers to the synthesis method of trisubstituted phosphine oxide and diphosphine oxide, especially refers to the green synthesis method of preparing trisubstituted phosphine oxide and dioxophosphine compound by reacting alkoxyphosphine with alcohol under the catalysis of iodine salt . Background technique [0002] Trisubstituted phosphine oxide compounds can be very conveniently reduced to trisubstituted phosphine compounds, and can be widely used as ligands in transition metal-catalyzed coupling reactions and asymmetric catalytic synthesis, and trisubstituted phosphine oxide or trisubstituted phosphine compounds can also be Directly as a catalyst to catalyze certain organic reactions. Trisubstituted phosphine oxide structures exist in natural products and pharmacologically active compounds. Therefore, the synthesis of trisubstituted phosphine oxide compounds has also attr...

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Problems solved by technology

[0003] The existing methods for preparing trisubstituted phosphine oxide compounds are mainly prepared by oxidizing the corresponding trisubstituted phosphine compound, but the trisubstituted phosphine compound needs to be synthesized in multiple steps and the price is high, so this method does not have practical application value

Trisubstituted phosphine oxide compounds can also be synthesized by Arbuzov under high temperature conditions of halogenated hydrocarbons and alkoxyphosphine, but it is necessary to use halogenated hydrocarbons with high toxicity and poor stability as alkylating reagents, and the reaction will produce activity Small molecular halogenated hydrocarbons with high and low boiling points are by-products, causing pollution

In recent years, there are transition metal catalyzed coupling methods, but transition metal catalysts are relatively expensive, and at the same time, ligands and a large amount of alkali need to be added to the reaction, resulting in many by-products and large pollution.

There are also literatures reporting a step-by-step method, in which an alkyl phosphine oxide is prepared in advance, and then an intramolecular rearrangement reaction occurs under the catalysis of a Lewis acid to realize the synthesis of a trisubstituted phosphine oxide, but the step-by-step reaction cycle is long and requires a large amount of separation and purification work , the efficiency is low, and a large number of by-products will be produced in this process, resulting in low atom economy and pollution

Therefore, these methods still have many shortcomings, which need to be improved urgently.

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