Synthesis using pyridinium anhydrobases,preparation of indolizine derivatives

A number of derivatives of indolizine ring system have been prepared from 1-substituted 4,6-diphenyl-2-phenacylidene-1,2-dihydropyridines either by metallation with LDA or acylation and further basic treatment. Similarly, I-arylmethyl-4,6-diphenyl-2-dicyanomethylene-1,2-dihydropyridines by action of LDA undergo cyclization to the corresponding 2-amino-1-cyano-3-aryl indolizines.     

Synthesis of 1-(1-Aroyl-2-arylvinyl)-2-dicyanomethylen-1,2-dihydropyridines from 2-Chloropyridinium Salts and Unsaturated Nitriles

1-(1-Aroyl-2-arylvinyl)-2-dicyanomethylene-1,2-dihydropyridines are formed from 1-(aroylmethyl)-2-chloropyridinium bromides and arylmethylenemalonitriles in ethanol at room temperature in the presence of a twofold excess of triethylamine. The products are converted into 2-amino-3-aroyl-1-cyanoindolizines on boiling in acetic acid.     

Recyclization of 1-amino-3.5-diaryl-2.6,6-tricyanocyclohexa-1,3,-dienes to pyridine derivatives

The base-catalyzed recyclization of 1-amino-3,5-diaryl-2,6, 6-tricyanocyclohexa-1,3-dienes to 2,4-diaryl-5-cyano-6-dicyanomethylene-1,2,3,6-tetrahydropyridines, 4,6-diaryl-3-cyano-2-dicyanomethylene-1,2-dihydropyridines, and 4,6-diaryl-3-cyano-2-dicyanomethylpyridines has been investigated. The intermediate products of this reaction — cis, trans-2-amino,4,6-diaryl-1,1,3-tricyanohexa-1,3,5-trienes —have been isolated; on heating these are transformed reversibly into the initial cyclohexadienes or they isomerize irreversibly into trans, trans-hexatrienes, while in the presence of a base (piperidine, diethylamine, triethylamine, KOH), they cyclize to form the above-mentioned' pyridine derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, PP. 621–625, May, 1986.     

One stage synthesis of 5-dicyanomethylene-3,5-dihydro-2h-benzimidazoles

Oxidative condensation of ketones, o-phenylenediamines, and malononitrile in the presence of acid catalysts and MnO₂ gives 5-dicyanomethylene-2-R-2-R-3,5-dihydro-2H-benzimidazoles. Changing the mono ketones to 1,5-diketones leads to 8-dicyanomethylene-3,4,4a,8-tetrahydropyrido[1,2-a]benzimidazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1494–1497, November, 1992.     

X-ray diffraction study of 1-[1-benzoyl-2-(2-furyl)vinyl]-2-dicyanomethylene-1,2-dihydropyridine

1-[1-Benzoyl-2-(2-furyl)vinyl]-2-dicyanomethylene-1,2-dihydropyridine was studied by X-ray structural analysis. The compound under study occurs as aZ isomer with respect to the central vinyl fragment.     

Synthesen mit Nitrilen, 24. Mitt.: Über Dicyanmethylen-pyrrolidine

Zusammenfassung Die Kondensationsprodukte des dimeren Malonsäurenitrils mit Benzil erleiden unter dem Einfluß von Alkalien eine Cyclisierung und zugleich 1,2-Arylverschiebung; so werden 2-Dicyanmethylen-5-oxo-4,4-diphenyl-pyrrolidin-3-carbonitrile erhalten.

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Syntheses with nitriles, XXIV.: Dicyanomethylenepyrrolidines

The condensation products of dimeric malononitrile and benzil on treatment with alkali undergo cyclization with concomitant 1.2-shift of the phenyl groups. The reaction products are 2-dicyanomethylene-5-oxo-4.4-diphenylpyrrolidine-3-carbonitriles.

     

Synthesis and structures of 1-[1-(4-R-benzoyl)-2-ethoxyvinyl]-2-dicyanomethylene-1,2-dihydropyridines

The reaction of (4-R-benzoyl)(2-bromopyridinitim) methylides with ethoxyrnethylene-rnalononitrile is stereoselective and affords Z-1-[1-(4-R-benzoyl)-2-ethoxyvinyl]-2-dicyationietliylene-1,2-dihydropyridines. The structure of 1-[1-(4-chlorobenzoyl)-2 ethoxyvinyll-2-dicyanomethylene-1,2-dihydropyridine has been established by X-ray structural study.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 434–436, February, 1996.     

两种荧光LB膜的制备和光谱性能

制取了４－二氰基亚甲基－２－甲基－６－对二甲胺基苯乙烯基－４Ｈ－吡喃（ＤＣＭ）和１，２－双（５－甲基苯并恶唑）基乙烯（ＤＴ）两种荧光分子的ＬＢ膜以及两者的混合膜，以吸收光谱和荧光光谱探讨了膜中分子的构型，微环境，发光性能等特征，发现在ＬＢ膜的缀密排布环境中ＤＣＭ顺式构型的含量较之在溶液中大为增加。     

6,6-Dimethyl-4,8-dioxospiro[2.5]octane-1,1,2,2-tetracarbonitrile in the synthesis of heterocyclic compounds of the 2,3-dihydrofuran and 5,6,7,8-tetrahydro-4h-chromene series

6,6-Dimethyl-4,8-dioxospiro[2.5]octane-1,1,2,2-tetracarbonitrile (III), synthesized by the interaction of tetracyanoethylene with 2-bromo-5,5-dimethyl-1,3-cyclohexanedione, reacts with alcohols and ketoximes to form 2-alkoxy-2-(3-alkoxycarbonyl-2,2-dimethylpropyl)-5-amino-3-dicyanomethylene-4-cyano-2,3-dihydrofurans and 2-alkylidenaminoxy-2-(3-alkylidenaminoxycarbonyl-2,2-dimethylpropyl)-5-amino-3-dicyanomethylene-4-cyano-2,3-dihydrofurans. Compound III with triarylphosphines forms 2-(triarylphosphoranilidenamino)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3,4,4-tricarbonitriles. Chuvash State University, Cheboksary 428015, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 170–181, February, 1998.     

Photoreaction of 9-dicyanomethylene-1,2,3,4-tetrahydro-1,4-methanonaphthalene: the 1,3-carbon migrations and the ethylene extrusion to dicyanoisobenzofulvene

Irradiation of 9-dicyanomethylene-1,2,3,4-tetrahydro-1,4-methanonaphthalene gave 3,3-dicyano-1,2,3,8b-tetrahydrocyclopent [a] indene and 2-dicyanomethylene-2H-indene.     

Synthesen mit Nitrilen, 21. Mitt.: Anomalien bei der Reaktion von Dicyanolefinen mit Hydrazin

Zusammenfassung Es wird gezeigt, daß bei der Umsetzung von 9-Dicyanmethylen-9,10-dihydro-10-phenanthrenon mit asymm. Dimethylhydrazin dasselbe Hydrazino-(2-oxo-1,2-dihydro-phenanthryliden)-essigsäuredinitril entsteht, wie bei der Umsetzung von unsubstit. Hydrazin. Ein Mechanismus dieser Reaktion, bei welcher es zu einer Ablösung von zwei Methylgruppen kommt, wird an Hand der gaschromatographisch nachgewiesenen Folgeprodukte diskutiert.

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Hydrazino-(2-oxo-1,2-dihydrophenanthrylidene)-acetodinitrile was formed in the reaction of 9-dicyanomethylene-9,10-dihydro-10-phenanthren-one with asymmetric dimethylhydrazine as well as in the reaction with unsubstituted hydrazine. The mechanism of this reaction involving the removal of two methyl groups is discussed on the basis of secondary reaction products detected byGLC.

     

Combining chlorination and sulfuration strategies for high-performance all-small-molecule organic solar cells

Three small-molecule donors based on dithieno [2,3-d:2’,3 ’-d’]-benzo[1,2-b:4,5-b’] dithiophene(DTBDT)unit were designed and synthesized by side chain regulation with chlorinated or/and sulfurated substitutions(namely ZR1,ZR1-Cl,and ZR1-S-Cl respectively),along with a crystalline non-fullerene acceptor IDIC-4 Cl with a chlorinated 1,1-dicyanomethylene-3-indanone(IC) end group.Energy levels,molar extinction coefficients and crystallinities of three donor molecules can be effectively altered by combining chlorination and sulfuration strategies.Especially,the ZR1-S-Cl exhibited the best absorption ability,lowest higher occupied molecular orbital(HOMO) energy level and highest crystallinity among three donors,resulting in the corresponding all-small-molecule organic solar cells to produce a high power conversion efficiency(PCE) of 12.05% with IDIC-4 Cl as an acceptor.     

Theoretical study on the mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile catalyzed by lithium ethoxide

The The mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile for the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2,5-dihydrofuran-3-carbonitrile catalyzed by lithium ethoxide was investigated by density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-31G(d) level. The vibration analysis and the IRC analysis verified the authenticity of transition states. The reaction processes were confirmed by the changes of charge density at the bond-forming critical point. The results indicated that lithium ethoxide is an effective catalyst in the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2, 5-dihydrofuran-3-carbonitrile from malononi-trile and 3-hydroxy-3-methyl-2-butanone. The activation energy of the reaction with lithium ethoxide was 115.86 kJ·mol⁻¹ less than the uncatalyzed reaction. The mechanism of the lithium ethoxide catalyzed reaction differed from the mechanism of the uncatalyzed reaction.     

5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2, 5-酮的拆分, 及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮 4(E)和4(Z)的合成, 并对它们的光致变色特性进行了初步研究。     

Preparation of Cyan Dyes from 6-Diethylaminobenzo[b]furan-2-carboxaldehyde

6-Diethylaminobenzo[b]furan-2-carboxaldehyde was synthesized in four steps and 48% overall yield starting from 4-diethylaminosalicylaldehyde. Five cyan dyes were made from this aldehyde using malononitrile dimer and 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran. The crystal structures of two dyes are included.     

Reactions of some 4-dicyanomethylenepyran derivatives with malononitrile and hydrazines

4-Dicyanomethylene-2-phenyl-4H-benzo[b]pyran, the corresponding thiapyran, and 4-dicyanomethylene-2,6-diphenyl-4H-pyran react with malononilrile under basic conditions to give 5-amino-4-cyano-2-phenylbenzo[b]pyrano[4,3,2-de] [1,6]naphthyridine, the corresponding thia-pyranonaphthyridine derivative, and 5-amino-6-cyano-2,8-diphenylpyrano[4,3,2-de] [1,6]naphthyridine, respectively. Certain other related reactions were studied in the course of investigating the above reactions. Hydrazine hydrate and 4-dicyanomethylene-2-phenyl-4H-benzo[b]pyran gave 5-(2-hydroxyphenyl)-3-phenylpyrazole, and phenylhydrazine gave 5-(2-hydroxyphenyl)-1,3-diphenylpyrazole.     

Studies in spiroheterocycles. Part XVII. synthesis of novel fluorine containing spiro[indole-pyranobenzopyran] and spiro[indenopyran-indole] derivatives

An elegant one-step synthesis of two novel spiro ring systems viz: spiro[3H-indole-3,4′-(2′-amino-3′-carbonitrile-[4′H]-pyrano[3,2-c]benzopyran)]-2,5′(1H)-dione8 and spiro[(2-amino-3-carbonitrile-indeno[1,2-b]pyran)-4(5H)>3′-[3H]indole]-2′,5(1′H)-diones in 80–85% yields is described. The spiro heterocycles were prepared by the reactions of fluorine containing 3-dicyanomethylene-2H-indol-2-ones with 4-hydroxy-2H-1-benzopyran-2-one and 1H-indene-1,3(2H)-dione respectively. The synthesized compounds have been characterized on the basis of elemental analyses, ir, pmr, ¹⁹F nmr and mass spectral data.     

An Efficient Procedure for the Synthesis of Spiro (3H-Indole-3,4′ (1′H)pyrano[2,3-C]pyrrole]-5′-carbonitriles Using Solid Inorganic Supports and Microwave Activation

Microwave irradiation accelerates the Michael condensation of 3-dicyanomethylene-2H-indole-2-one with 2-pyrrolidone/ N-methy1-2-pyrrolidone (i) adsorbed on neutral alumina in “dry media” (ii) using absolute ethanol as energy transfer medium. 3-Dicyanoniethylene-2H-indol-2-one was synthesized under microwave irradiation using indole-2,3-dione and malononitrile. The results were compared with those obtained following the classical method. The advantages obtained by the use of microwave irradiation are demonstrated.     

Dicyanmethylen-acenaphthenon-hydrazone — Polymethine mit dem Amino-dicyanallylidenimin-Chromophor

Acenaphthenequinone reacts with malononitrile and asymm. substituted hydrazines to deeply coloured 2-dicyanomethylene-1-acenaphthenone-hydrazones. They are classified as aza-cyanine type polymethine dyes with the amino-dicyanoallylidenimide chromophore.     

Synthesis and crystal structure of 5-amino-4,6-dicyano-3-dicyanomethylene-1, 8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene

5-Amino-4,6-dicyano-3-dicyanomethylene-1,8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene has been synthesized. The molecular and crystal structure of this compound has been determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–172, January, 1996.