Spiro heterocyclization of 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles to 3H-pyrrole derivatives, 2-oxa-7-azaspiro[4.4]nona-3,6,8-trienes

Belikov, М. Yu.; Ершов, О. В.; Lipovskaya, I. V.; Федосеев, С. В.; Насакин, О. Е.

doi:10.1134/s1070428013060110

Cited by 16 publications

(8 citation statements)

References 10 publications

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“…20 We have found that multifunctional 3H-pyrrole derivatives are formed by the reaction of compounds containing the vicinal dinitrile moiety, namely 4-oxoalkane-1,1,2,2-tetracarbonitriles with morpholine. Depending on the structure of 4-oxoalkane-1,1,2,2-tetracarbonitriles, both 3H-pyrrole-3,4-dicarbonitriles 21,22 and 3H-pyrroles spiro-fused with the furan ring [23][24][25][26] were obtained by this method. The main criterion for the formation of 3H-pyrrole ring in this process is the presence of a proton in the α-position to one of the cyano groups of the starting 4-oxoalkane-1,1,2,2-tetracarbonitriles.…”

Section: Syntheses Based On Oximesmentioning

confidence: 99%

Synthesis of 3H-pyrroles (microreview)

Belikov

Ершов

2016

Chem Heterocycl Comp

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Section: Syntheses Based On Oximesmentioning

confidence: 99%

Synthesis of 3H-pyrroles (microreview)

Belikov

Ершов

2016

Chem Heterocycl Comp

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“…37 This is the first case when salts of this type with organic cations have been isolated and characterized, although their presence has been implied at the initial stage of many transformations of 4-oxoalkane-1,1,2,2-tetracarbonitriles in basic media. 35,[38][39][40][41] Compounds 3a-c were found to be unstable in solutions, therefore suitable NMR spectra could not be acquired. The actual spectra contained a multitude of signals, which could not be assigned.…”

mentioning

confidence: 98%

“…A similar situation was earlier described by us for analogs of compounds 4. 35,36 The synthesized spiranes 4b,d, containing a potentially photosensitive 1,2-diarylethene fragment, were found to be photochromic (Scheme 4). The irradiation of colorless solutions in MeCN with UV light at 312 nm caused the formation of colored photoinduced form 9b,d.…”

mentioning

confidence: 98%

“…34 At the same time, it is known that 4-oxoalkane-1,1,2,2-tetracarbonitriles based on some aliphatic and alkylaromatic ketones react with amines forming spiro compounds, containing an alkylarylethene or dialkylethene fragment. 35,36 The introduction of tetracyanoethylated 1,2-diaryl ketones into these reactions allows to obtain DAE with spirofusion at the ethene linker.…”

mentioning

confidence: 99%

“…It is known that adducts of TCNE with other 1-phenyl ketones can be converted to spiro compounds by the action of amines. 35 The next step in the synthesis of DAE with spirofusion in the ethene bridge structure was the interaction of compounds 2а,b with morpholine. The final products of this reaction were identified as 8-amino-4-aryl-1-imino-6-(morpholin-4-yl) -3-phenyl-2-oxa-7-azaspiro[4.4]-nona-3,6,8-triene-9-carbonitriles 4а,b (Scheme 1).…”

mentioning

confidence: 99%

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Directed synthesis of new spiro-fused photochromes of diarylethene series

Belikov

Ievlev

Belikova

et al. 2015

Chem Heterocycl Comp

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518Diarylethenes (DAE, dihetarylethenes) are subject to intense study due to the possibility of using these compounds as photosensitive components in various applications, in particular, information processing, 1-4 optical switches for organic electronics, 5-7 and biosensors. 8 The potential for practical applications of DAE in the indicated areas motivate synthetic studies of photochromes with precisely designed photophysical parameters, such as thermal stability of the photoinduced form, 9-15 quantum yield of the forward and reverse photoreaction, 16-20 and the phototransformation cyclicity. 21-24 An important direction of study, with the goal of improving the practical characteristics of DAE, is the development of synthetic methods for obtaining DAE with intramolecular noncovalent interactions and steric hindrance. 25-31 One of the methods for creating a non-covalent interaction in DAE is the introduction of spiro-fused structures at the ethene linker. We should note that only isolated examples of spirofused DAE are known. 31-33 However, based on the current data, it is expected that the presence of spiro-fused moiety at the ethene linker could be used to confer certain useful properties to DAE. For example, some of the best forward quantum reaction yields have been demonstrated for spirofused DAE specifically due to the non-covalent interaction, caused by the presence of spirofusion. 31 By introducing or removing spirofusion it may be possible to tune the ability of DAE to undergo photochromic transformations. 32 The introduction of spirofusion may also be used for the preparation of DAE with several photoswitchable fragments. 33 The presented data show the importance of developing new approaches to the synthesis of diarylethenes featuring a rare combination of structural moieties, in particular spiro-fused systems. With this in mind, we set out to expand the range of available methods for the synthesis of DAE with spirofusion at the ethene linker.Recently we demonstrated a new approach to the synthesis of photochromic DAE, based on the transformations of intermediates obtained by reactions of tetracyanoethylene (TCNE) with 1,2-diarylethanones, namely, 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. 34 At the same time, it is known that 4-oxoalkane-1,1,2,2-tetracarbonitriles based on some aliphatic and alkylaromatic ketones react with amines forming spiro compounds, containing an The reaction of tetracyanoethylated 1,2-diarylethanones with morpholine was used for directed synthesis of spiro-fused diarylethenes, 8-amino-1-imino(oxo)-6-morpholino-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles. The intermediates in this process were tetracyanoalkanone salts. The formation of spiranes was sensitive to the nature of aromatic substituents at the carbonyl group of 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. The obtained spiro-fused diarylethenes exhibited photochromic properties.

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