Reactions of pregnenolone and 16-dehydropregnenolone acetate with tetracyanoethylene

Belikov, М. Yu.; Ершов, О. В.; Eremkin, A. V.; Kayukov, Ya. S.; Насакин, О. Е.

doi:10.1134/s1070428010070225

Cited by 5 publications

(6 citation statements)

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“…Analogous salts containing metal and ammonium ions as cationic species have been reported [4][5][6]. Salts A undergo further transformations by the action of excess morpholine.…”

Section: Short Communicationsmentioning

confidence: 99%

“…It is known that 4-oxoalkane-1,1,2,2-tetracarbonitriles react with nitrogen-centered nucleophiles, such as ammonia and amines, to give 3-amino-7-oxo-4,6-diazabicyclo[3.2.1]oct-2-ene-1,2-dicarbonitriles [1], 3-amidinio-2-aminopyridine-4-carboxylates [2], diethylammonium 3,4-dicyano-5,6,7,8-tetrahydroquinolin-2-olates [3], and ammonium 4-aryl-4-oxo-1,1,2-tricyanobut-2-en-1-ides [4]. However, these results do not allow us to draw a definite conclusion on the direction of attack by N-nucleophiles on the reaction centers in polyelectrophilic 4-oxoalkane-1,1,2,2-tetracarbonitriles.…”

Section: Short Communicationsmentioning

confidence: 99%

“…

SHORT COMMUNICATIONSIt is known that 4-oxoalkane-1,1,2,2-tetracarbonitriles react with nitrogen-centered nucleophiles, such as ammonia and amines, to give 3-amino-7-oxo-4,6-diazabicyclo[3.2.1]oct-2-ene-1,2-dicarbonitriles [1], 3-amidinio-2-aminopyridine-4-carboxylates [2], diethylammonium 3,4-dicyano-5,6,7,8-tetrahydroquinolin-2-olates [3], and ammonium 4-aryl-4-oxo-1,1,2-tricyanobut-2-en-1-ides [4]. However, these results do not allow us to draw a definite conclusion on the direction of attack by N-nucleophiles on the reaction centers in polyelectrophilic 4-oxoalkane-1,1,2,2-tetracarbonitriles.

While continuing studies on reactions of tetracyanoethylated ketones with N-nucleophiles, we found that 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles Ia-Ic react with morpholine to produce 80-93% of previously unknown 5-amino-3-(2-aryl-2-oxoethyl)-2-morpholino-3H-pyrrole-3,4-dicarbonitriles IIa-IIc.

Presumably, the initial step in this reaction is formation of morpholinium salt A with CH acid Ia-Ic.

…”

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confidence: 99%

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Synthesis of 5-amino-3H-pyrrole-3,4-dicarbonitriles from 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles

et al. 2011

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“…Analogous salts containing metal and ammonium ions as cationic species have been reported [4][5][6]. Salts A undergo further transformations by the action of excess morpholine.…”

Section: Short Communicationsmentioning

confidence: 99%

Section: Short Communicationsmentioning

confidence: 99%

“…

Presumably, the initial step in this reaction is formation of morpholinium salt A with CH acid Ia-Ic.

…”

mentioning

confidence: 99%

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Synthesis of 5-amino-3H-pyrrole-3,4-dicarbonitriles from 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles

et al. 2011

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“…The reactions of heterocyclization resulting in derivatives of dihydrofuran , dihydropyrrole , pyrrole , pyridine , and tetrahydroquinoline are typical for the derivatives of the polycanocompounds, in particular acyltetracyanoalkanes and acyltetracyanocyclopropanes. However, information on the heterocyclization of the 1,1,2,3,3‐pentacyanopropenide anion is rather limited.…”

Section: Introductionmentioning

confidence: 99%

Hydrolytic Heterocyclization of the 1,1,2,3,3‐Pentacyanopropene Salts

Khil

Kaminskii

Slabko

et al. 2014

Journal of Heterocyclic Chem

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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.…”

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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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Reactions of pregnenolone and 16-dehydropregnenolone acetate with tetracyanoethylene

Cited by 5 publications

References 7 publications

Synthesis of 5-amino-3H-pyrrole-3,4-dicarbonitriles from 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles

Synthesis of 5-amino-3H-pyrrole-3,4-dicarbonitriles from 4-aryl-4-oxobutane-1,1,2,2-tetracarbonitriles

Hydrolytic Heterocyclization of the 1,1,2,3,3‐Pentacyanopropene Salts

Directed synthesis of new spiro-fused photochromes of diarylethene series

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