Reactions of tetracyano-1,4-dithiin and tetracyanothiophene with nucleophiles: synthesis of tetracyanopyrrole and tetracyanocyclopentadiene salts

Simmons, Howard E.; Vest, Robert D.; Vladuchick, S. A.; Webster, Owen W.

doi:10.1021/jo01313a019

Cited by 40 publications

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“…Weakly basic anions are candidates for anionic PTCs because they barely undergo protonation or react with other cationic species. Tetracyanocyclopentadienides (C 5 R(CN) 4 − ) [19][20][21] are weakly basic anions; their conjugate acids exhibit very small pK a values as superacids, e.g., perchloric acid. 22,23) Recently, we have efficiently synthesized…”

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confidence: 99%

Acceleration of Acid-Catalyzed Hydrolysis in a Biphasic System by Sodium Tetracyanocyclopentadienides

Sakai

Bito

Itakura

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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The hydrolysis of tert-butyldimethylsilyl L-menthyl ether (3) in a CH 2 Cl 2 -1 M HCl biphasic solvent system was accelerated by the addition of sodium tetracyanocyclopentadienides 1. Particularly, the reaction rate was enhanced using sodium salt 1a-c with a lipophilic substituent on the cyclopentadienide ring. From the results obtained by a triphasic experiment, hydrolysis proceeds via the formation of hydronium ion 2 in the aqueous phase by ion exchange, followed by the transfer of 2 to the CH 2 Cl 2 phase.Key words phase-transfer reaction; hydrolysis; tetracyanocyclopentadienide; acid-catalyzed reaction Phase-transfer reactions have garnered increasing attention in organic chemistry because of their mild, sustainable conditions. 1) Phase-transfer catalysts (PTCs) enhance the reactivity of anionic reagents by forming a lipophilic ion pair, mediating a reaction in the organic phase or at the interface between two phases. Enantioselective phase-transfer reactions catalyzed by chiral quaternary ammonium salts are one of the representative methods for synthesizing optically active molecules.2,3) Anionic PTCs have also been developed for reactions where lipophilic anions enhance the solubility of the reactive cationic species, thereby promoting the reactions. Kobayashi et al. have reported the first anionic phase-transfer reaction using tetrakis(3,5-bis(trifluoromethyl) phenyl) borate (TFPB) anion. [4][5][6] Recently, asymmetric anionic phase-transfer reactions 7,8) have been reported using chiral phosphates with an aziridinium cation 9) and N-haloammonium cations. [10][11][12][13][14][15][16][17][18]

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confidence: 99%

Acceleration of Acid-Catalyzed Hydrolysis in a Biphasic System by Sodium Tetracyanocyclopentadienides

Sakai

Bito

Itakura

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Tetramethylammonium Tetracyanopyrrolide [Me 4 N]tcp: The procedure mainly follows that given in Ref. 25 with some modifications given in Part 1 of structural chemical studies of tetracyanopyrrolide.…”

Section: Methodsmentioning

confidence: 99%

Structural Chemistry of Tetracyanopyrrolide (Part 2): Spin Crossover in a Bis‐Tripodal Iron(II) Complex

Szafranowska¹,

Landvogt²,

Beck³

2015

Zeitschrift anorg allge chemie

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The mononuclear iron(II) complex [Fe(tpm)2]2+(tcp–)2 (1) containing the neutral tripodal N3‐donor ligand tris(pyrazol‐1‐yl)methane (tpm) and the mononegative tetracyanopyrrolide (tcp) as counter‐anion was characterized by X‐ray diffraction on twinned crystals and investigated in the solid state by magnetic susceptibility measurements and differential scanning calorimetry. Structural investigations at 123 K reveal Fe–N distances typical for low‐spin d6 iron(II). Compound 1 undergoes a gradual, incomplete spin crossover in the examined temperature range 1.9–400 K. Comparisons are made with known analogous [Fe(tpm)2]2+(X–)2 compounds bearing different anions X, which display similar crossover behavior.

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“…Much to my surprise, when I treated TCS1 with nitromethane under the same conditions I got mercaptotetracyanocyclopentadienide 34 (44). In other studies, I found that the action of cyanide on TCS1 forms decacyanooctatrienediide 34 (45). Wudl at University of California at Santa Barbara recently confirmed its structure by X ray and oxidized it to decacyanooctatetraene 35 (46) (E 1/2 vs SCE 0.92 V) (Scheme 22).…”

Section: Thiacyanocarbonsmentioning

confidence: 96%

“…32 Blomstrom 33 showed that oxidation of Bahr salt with SOCl 2 generates dicyanodithiete (41) (Scheme 20) on its way to TCS2. Vest 34 found that sodium azide reactes with TCS2 to give tetracyanopyrrole (42) isolated as its tetramethylammonium salt (Scheme 21). The mechanism of this transformation remains obscure.…”

Section: Thiacyanocarbonsmentioning

confidence: 99%

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Cyanocarbons: A classic example of discovery‐driven research

Webster

2001

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Cyanocarbons are organic compounds bearing enough cyano functional groups to significantly alter their chemical properties. For example, tetracyanoethylene forms a stable anion radical, is a strong acid, and readily substitutes its cyano groups. Tetracyanoethylene oxide reacts by addition across its carbon-carbon bond. Diazodicyanoimidazole cleaves nitrogen to form a superelectrophilic carbene, and pentacyanocyclopentadiene is about as acidic as perchloric acid. In this highlight, discovery-driven research that fanned out from tetracyanoethylene to a multiperson effort at DuPont on cyanocarbon chemistry is narrated.

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Reactions of tetracyano-1,4-dithiin and tetracyanothiophene with nucleophiles: synthesis of tetracyanopyrrole and tetracyanocyclopentadiene salts

Cited by 40 publications

References 0 publications

Acceleration of Acid-Catalyzed Hydrolysis in a Biphasic System by Sodium Tetracyanocyclopentadienides

Acceleration of Acid-Catalyzed Hydrolysis in a Biphasic System by Sodium Tetracyanocyclopentadienides

Structural Chemistry of Tetracyanopyrrolide (Part 2): Spin Crossover in a Bis‐Tripodal Iron(II) Complex

Cyanocarbons: A classic example of discovery‐driven research

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