Trifluoromethylmalononitrile. The reaction of 1,1-dichloro-2,2-dicyanoethylene with argentous fluoride

Josey, A. D.; Dickinson, C. L.; Dewhirst, Kenneth C.; McKusick, B. C.

doi:10.1021/jo01281a053

Cited by 40 publications

(7 citation statements)

References 4 publications

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“…Only one synthetic procedure for 6 has been described in the literature . In this procedure, a four‐step synthetic route affords 1,1‐dichloro‐2,2‐dicyanoethylene ( 12 ),, which is allowed to react with cyclopentadiene through a Diels–Alder reaction to provide the norbornene derivative 14 . Finally, treating 14 with potassium hydroxide gives 6 .…”

Section: Resultsmentioning

confidence: 99%

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Quant

Lennartson

Dreos

et al. 2016

Chemistry A European J

124

170

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Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol−1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg−1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.

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Section: Resultsmentioning

confidence: 99%

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Quant

Lennartson

Dreos

et al. 2016

Chemistry A European J

124

170

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“…The dimethylamino groups in 1 and 2 were replaced by diethylamino groups to enhance the solubility of the target dipolar chromophores without much sacrifice in their crystallinity 14. To introduce the cyano functionality in position 4 in compounds 4 , 6 , 7 , and 8 , dicyanovinyl ( 9 15) and tricyanovinyl chloride 10 16 were heated with appropriate ethynylanilines 11 17 and 12 to give the 4‐chlorinated buta‐1,3‐diene precursors 13 – 16 in 46–93 % yield. Substitution of the chloro substituent in 13 – 16 by cyano was achieved by Pd‐catalyzed reaction with CuCN/KCN18 to give the target molecules in low yields (5–32 %).…”

Section: Resultsmentioning

confidence: 99%

1,1‐Dicyano‐4‐[4‐(diethylamino)phenyl]buta‐1,3‐dienes: Structure–Property Relationships

et al. 2012

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We report the synthesis and physical study of a series of 1,1‐dicyano‐4‐[4‐(diethylamino)phenyl]buta‐1,3‐dienes in which the number and position of additional CN substituents along the 1,1‐dicyanobuta‐1,3‐dienyl fragment is systematically varied. While X‐ray analysis provided unambiguous information about molecular geometries in the crystal, UV/Vis and electrochemical measurements, by cyclic voltammetry (CV) and rotating disk voltammetry (RDV), revealed that introduction of additional cyano groups in the C2‐ and C4‐positions most affected the optical properties of these molecules in solution, in terms of intramolecular charge‐transfer absorption energy and intensity. A comparison with structurally related chromophores indicates that the shift of the anilino donor from position 2/3 to 4 along the butadiene scaffold results in a remarkable bathochromic shift of the ICT absorption maxima, mainly due to the higher planarity in the present series. These findings are further corroborated by density functional theory calculations. Preliminary nonlinear optical (NLO) measurements confirm the promise of the new push‐pull chromophores as third‐order nonlinear‐optical molecular materials.

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“…The analogous butatriene 93 which is obtained by condensation of I , 1 -bis(dimethylamino)ethylene ti6 with 1,1 -dichloro-2,2-dicyanoethylene 7 ' is considered as the cumulogue of 5 (Scheme 3).…”

Section: H Cnmentioning

confidence: 99%

Exceptionally short central bonds in the cumulogue and the vinylogue of 2,2-dicyano-1,1-bis(dimethylamino)ethylene

Tinant¹,

Declercq²,

Bouvy³

et al. 1993

J. Chem. Soc., Perkin Trans. 2

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The preparation and crystal structures of twofold push-pull butatriene 2-cyano-5,5-bis(dimethylamino)penta-2,3,4-trienentrile 9 and butadiene 2-cyano-5.5-bis(dimethylamino) penta-2.4-dienenitrile 4 with bis-dimethylamino and dicyano substituents are described. These compounds may be compared with the known corresponding ethylene derivative 1 ,I -dicyano-2,2-bis(dimethy1amino)ethylene 5. The exceptionally short central bonds in 9 and 4 are in agreement with the earlier proposed concept of cumulogy and of vinylogy to 5.Vinylogous activation of the methyl group by cyano substituents is much stronger than by ester substituents.' Thus, et hylidenemalononitrile I condenses with N,N-dimethyldichloromethyleneaminium chloride 22 to the new 2-chloro dienamine 3 whereas the diester analogue fails to react.' The substitution of the chlorine atom in 3 with N,N-dimethylamine leads to the twofold push-pull butadiene 43 (Scheme 1). Compound 4 is the vinylogue4 of the known I,l-dicyano-2,2bis(dimethy1amino)ethylene 5 (Scheme 2).

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Trifluoromethylmalononitrile. The reaction of 1,1-dichloro-2,2-dicyanoethylene with argentous fluoride

Cited by 40 publications

References 4 publications

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

1,1‐Dicyano‐4‐[4‐(diethylamino)phenyl]buta‐1,3‐dienes: Structure–Property Relationships

Exceptionally short central bonds in the cumulogue and the vinylogue of 2,2-dicyano-1,1-bis(dimethylamino)ethylene

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