Electro-synthesis method of bis(methanesulfonyl)peroxide

Abstract

The construction of a C-O bond through an aromatic electrophilic substitution reaction is a frontier subject in the field of organic synthetic chemistry, and the key point is to develop a new reaction reagent to realize a non-bio-enzyme catalyzed C-H bond oxygenation reaction. At present, bis(methanesulfonyl)peroxide as an oxidizing agent can chemically and selectively realize oxygenation reaction of aromatic Csp2-H bonds and benzyl Csp3-H bonds, but the bis(methanesulfonyl)peroxide is rare in suppliers and high in market price, and some serious defects exist in previous preparation methods. A novel electrochemical reaction device is designed, sodium methanesulfonate is generated in situ through an acid-base neutralization reaction, and then the sodium methanesulfonate is oxidized at an anode to generate bis(methanesulfonyl)peroxide; and meanwhile, the cathode generates high-energy-density clean energy hydrogen. The method has the main advantages of no need of additional addition of sodium methanesulfonate, no need of an E87-05S diaphragm, high product yield, simple electrode preparation, low process cost and the like.

Description

technical field [0001] The invention relates to an electrochemical preparation method of bis(methanesulfonyl) peroxide, which belongs to the technical field of organic electrosynthesis. Background technique [0002] Electrophilic aromatic substitution reaction (S E Ar) is the reaction in which the hydrogen atom on the aromatic ring system is replaced by an electrophile due to its high inherent reactivity, including nitration reaction, halogenation reaction, sulfonation reaction, and Friedel-Crafts reaction, which are used in organic chemistry to construct Common strategies for chemical bonds such as C-N, C-X, C-S, C-C, etc. However, similar C-O bond-forming reactions can only be catalyzed by natural cytochrome P450 enzymes. In general, it is difficult for complex small molecules to undergo non-enzymatic catalyzed C-H bond oxygenation of aromatic hydrocarbons, which may be due to the fact that oxygen radicals can induce hydrogen atom abstraction side reactions that can comp...

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Problems solved by technology

The disadvantages of this method are: methanesulfonyl chloride reacts very easily with compounds with active hydrogen, and the experimental reagents and atmosphere must be strictly dehydrated; hydrogen peroxide is not a sustainable oxidant, and the dosage is too large, which has potential safety hazards, etc.

[0009] a) Sodium methanesulfonate (CAS No. 2386-57-4) dissolves slowly in methanesulfonic acid, requires long-time stirring, and the dosage is large, and the market price is relatively high (1590￥ / Kg, purity 99%, ), leading to high raw material costs;

[0010] b) The diaphragm (CAS No. 1163733-25-2) is very expensive, the supply channel is too narrow, and it is easy to fall off and it is difficult to fix it on the plastic nozzle for a long time;

[0011] c) The DC current applied in the electrolytic cell is too large (500mA) and the time is long, which not only makes the Faraday efficiency low, but also the E87-05S diaphragm is easily damaged by strong current, and even has potential safety hazards, which may easily cause accidents;

[0012] d) The effective surface area of ​​the thin platinum wire as the reaction site is too small, which greatly reduces the reaction rate and catalytic efficiency

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