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Method for preparing aromatic alpha-diketone compound through electrochemical oxidation

A compound and electrochemical technology, applied in the field of preparation of carbonyl compounds, can solve problems such as harsh reaction conditions and toxic reagents, and achieve the effects of green and mild reaction conditions, avoiding excessive oxidation and passivation

Active Publication Date: 2021-12-07
SOUTHWEST UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the above methods can successfully synthesize α-diketones, most of them still have some disadvantages, such as the use of stoichiometric or excessive amounts of strong oxidizing agents, toxic reagents, transition metals, harsh reaction conditions, etc.

Method used

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  • Method for preparing aromatic alpha-diketone compound through electrochemical oxidation
  • Method for preparing aromatic alpha-diketone compound through electrochemical oxidation
  • Method for preparing aromatic alpha-diketone compound through electrochemical oxidation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Preparation of aromatic α-diketone compound 1,2-Diphenylethanedione (Ⅱ-1), its structural formula is:

[0041]

[0042] The specific preparation method is as follows:

[0043] Add 0.25 mmol of compound I-1 (diphenyl ethyl ketone) as a reaction substrate to an electrochemical device (anode: a carbon rod with a diameter of 0.5 cm, a cathode: a platinum sheet with a specification of 1 cm x 1 cm x 0.2 mm), Add 0.125mmol additive triethylenediamine (DABCO), 0.375mmol electrolyte n-tetrabutylammonium iodide (nBu 4 NI) and 6mL reaction solvent acetonitrile, at room temperature with the current energization of 7mA, carry out reaction 6.5h, after reaction finishes, separate and obtain 39.4mg by silica gel column chromatography (eluent is sherwood oil:ethyl acetate=150:1) The yellow solid was the target compound II-1 (yield: 75%, Mp: 94.5-95.5°C).

[0044] 1 H NMR (600MHz, CDCl 3 ) δ 7.98 (dd, J = 8.4, 1.4Hz, 4H), 7.65 (t, J = 7.4Hz, 2H), 7.51 (t, 12Hz, 4H).

[0045] 13 ...

Embodiment 2

[0047] Preparation of aromatic α-diketone compound 1-(2-methoxyphenyl)-2-phenylethane-1,2-dion (II-2), its structural formula is:

[0048]

[0049] The specific preparation method is as follows:

[0050] Add 0.25 mmol of compound I-2 (1-(2-methoxyphenyl)-2-phenylethanone) as a reaction substrate to an electrochemical device (anode: carbon rod with a diameter of 0.5 cm, cathode: specification 1cm x 1cm x 0.2mm platinum sheet), add 0.125mmol additive triethylenediamine (DABCO), 0.375mmol electrolyte n-tetrabutylammonium iodide (nBu 4 NI) and 6mL reaction solvent acetonitrile, at room temperature with the current energization of 7mA, carry out reaction 6.5h, after reaction finishes, separate and obtain 44.4mg by silica gel column chromatography (eluent is sherwood oil:ethyl acetate=150:1) The yellow solid was the target compound II-2 (yield: 74%, Mp: 70.5-71.5°C).

[0051] 1H NMR (600MHz, CDCl3) δ8.03(d, J=7.7Hz, 1H), 7.93(d, J=7.7Hz, 1H), 7.61(q, J=8.7, 8.1Hz, 2H), 7.49(t ...

Embodiment 3

[0054] Preparation of aromatic α-diketone compound 1-(4-methoxyphenyl)-2-phenylethane-1,2-dione (II-3), its structural formula is:

[0055]

[0056] The specific preparation method is as follows: 0.25mmol compound I-3 (1-(4-methoxyphenyl)-2-phenylethanone) is added to the electrochemical device (anode: 0.5cm in diameter) as a reaction substrate carbon rod, cathode: platinum sheet with a specification of 1cm x 1cm x0.2mm), add 0.125mmol additive triethylenediamine (DABCO), 0.375mmol electrolyte n-tetrabutylammonium iodide (nBu 4 NI) and 6mL reaction solvent acetonitrile, at room temperature with the current energization of 7mA, carry out reaction 6.5h, after reaction finishes, separate and obtain 38.4mg by silica gel column chromatography (eluent is sherwood oil:ethyl acetate=150:1) The yellow solid was the target compound II-3 (yield: 64%, Mp: 60.1-62.2°C).

[0057] 1 H NMR (600MHz, CDCl 3 )δ7.96(dd, J=13.7,8.1Hz,4H),7.67–7.61(m,1H),7.50(t,J=7.5Hz,2H),6.97(d,J=8.4Hz,2H),...

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Abstract

The invention relates to a method for preparing an aromatic alpha-diketone compound through electrochemical oxidation, and belongs to the technical field of carbonyl compound preparation. The invention discloses a method for preparing an aromatic alpha-diketone compound through electrochemical oxidation. The method uses an electrochemical oxidation means, provides reaction power through a new benzyl position C-H bond carbonylation method, uses current to provide reaction power, uses gain and loss of electrons on an electrode as a redox agent, avoids the use of an additional stoichiometric redox agent, and has green and mild reaction conditions. In addition, in order to avoid the situation that free radical intermediates generated in the reaction process are polymerized on the surfaces of the electrodes, so that the electrodes are passivated, and the electrolysis efficiency is reduced, corresponding electrolyte is selected, the solvent conductivity is improved, meanwhile, the electrolyte can serve as a reaction medium additionally, excessive oxidation of a substrate is avoided, and the passivation phenomenon of the electrodes is avoided; and more importantly, free radicals generated by oxidation can be used as a hydrogen atom transfer reagent in the reaction process, so that one substance has multiple purposes, and the atom economy is relatively high.

Description

technical field [0001] The invention belongs to the technical field of preparation of carbonyl compounds, and relates to a method for preparing aromatic α-diketone compounds by electrochemical oxidation. Background technique [0002] Aromatic α-diketone structures widely exist in natural products and bioactive molecules (breast cancer cell proliferation inhibitors (15,16-Dihydrotanshinone I, Cryptotanshinone, Tanshinone VI, Tanshindiol C) and the first naturally occurring dibenzoylcarboside Vijayosin). Aromatic α-diketone compounds are also versatile synthetic intermediates, widely used to construct complex structures, such as for the synthesis of biologically active compounds, heterocyclic compounds, photoactive materials γ-butyrolactone, cyclopropane derivatives and various Ligands of metal complexes, etc. In addition, aromatic α-diketones can also be used as acylating agents in photochemical reactions, and are often used as photoinitiators in polymer chemistry. Therefo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/05C25B3/07C25B3/09C25B3/23
CPCC25B3/07C25B3/09C25B3/05C25B3/23Y02E60/10
Inventor 何延红官智陈圆李瑞雪
Owner SOUTHWEST UNIVERSITY
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