Electrochemical synthesis of new organic compounds based on the oxidation of 1,4-dihydroxybenzene derivatives in the presence of primary and secondary amines

Abstract

An efficient method for the synthesis of 2-benzyl(4-hydroxyphenyl)amino)-6-(benzylamino)-p-benzoquinone derivatives and 2,5-bis-benzyl(methyl)amino)-p-benzoquinone based on the Michael type reaction is described. The electrochemically generated p-benzoquinone reacted with benzylamine derivatives (primary amines) and N-methylbenzylamine (a secondary amine), respectively, to produce the final products. In this work, some new symmetric and asymmetric p-benzoquinone derivatives are synthesized using green solvents with high yields.

Efficient electrochemical synthesis of robust, densely functionalized water soluble quinones

“…10 The resulting hydroquinones can undergo electrochemical oxidation to the corresponding benzoquinones at potentials determined by their substituents. 11 Electrochemical oxidation of hydroquinones and catechols in the presence of nucleophiles has been demonstrated previously to form substituted quinone products, [12][13][14][15] but this process commonly leads to addition of a single nucleophile due to the higher reduction potential of the quinone following nucleophile addition. 16 Addition of a thiol, however, lowers the potential of the resulting thioether quinone by approximately 20 mV.…”

Green electro-organic synthesis of a novel catechol derivative based on o-benzoquinone nucleophilic addition

“…The multi-CVs of a 5 mM solution of 1 in water/ethanol (50/50) containing phosphate buffer (0.10 M, pH 7.0) in the presence of 3) to form the triazinone 9. 1,11,45,48,49 5 mM of 3 were also recorded (Fig. 3).…”

“…This is a result of the oxidation potentials 6 and 7 being very close to the oxidation potential of the starting catechol ( 1 ). 1,11,45,48,49…”

“…Based on the above results, We noted that the first EC mechanism 8,36 of the 1,2-Michael addition reaction of 3 and o -benzoquinone ( 2 ) (Scheme 4) is much faster than other side reactions, leading presumably to intermediate 6 . 1,11,45,48,49 Additionally, compound 6 oxidation is easier than the oxidation of the parent starting molecule 1 because of the existence of an electron-donating group, 45,49,51 with the formation of an intermediate 7 . Following this, the nucleophilic NH 2 quickly attacks via the second EC mechanism, 8,36,37 in a second 1,2-Michael addition, through the formation of intermediate 8 , which is reduced to form product 9 .…”

Electrochemical strategies for C–H functionalization and C–N bond formation

“…[675][676][677][678][679][680][681] Considering their relatively low oxidation potentials, it is perhaps unsurprising that an assortment of nucleophiles are compatible with these processes without being subjected to oxidation. Here, amines, [682][683][684][685][686][687][688][689] azide, 690,691 enolates and other carbon nucleophiles, [692][693][694][695][696][697][698][699][700][701][702][703][704][705][706][707][708][709][710][711] nitrate, 712 sulfinates [713][714][715][716][717][718][719][720][721][722][723]…”