2450-55-7Relevant academic research and scientific papers
Facile synthesis of substituted fumaronitriles and maleonitriles: Precursors to soluble tetraazaporphyrins
Fitzgerald,Taylor,Owen
, p. 686 - 688 (1991)
Alkynes are converted in good yield to alkyl and/or aryl substituted fumaronitriles and maleonitriles, a rish source of precursors to soluble tetraazaporphyrins.
Reaction of bromopentafluorobenzene and pentafluorophenyllithium with α-lithiated arylacetonitriles
Refat, Hala Mohammed,Faddo, Ahmed A.,Biehl, Ed
, p. 99 - 103 (1996)
Bromopentafluorobenzene and pentafluorophenyllithium react with α-lithiated arylacetonitriles in ether to give α-aryl-2,3,5,6-tetrafluorophenylacetonitriles and α-aryl-4-bromo-2,3,5,6-tetrafluorophenylacetonitriles, respectively. However, the reaction of bromopentafluorobenzene with α-lithiated arylacetonitriles in ether/THF affords trans-1,2-dicyanostilbenes. Mechanisms for the formation of the various products are proposed.
Elusive ethynyl azides: Trapping by 1,3-dipolar cycloaddition and decomposition to cyanocarbenes
Banert, Klaus,Hagedorn, Manfred,Wutke, Jens,Ecorchard, Petra,Schaarschmidt, Dieter,Lang, Heinrich
supporting information; experimental part, p. 4058 - 4060 (2010/09/06)
Although they decompose rapidly to produce cyanocarbenes, ethynyl azides were generated from (chloroethynyl)arenes and trapped for the first time by 1,3-dipolar cycloaddition at cyclooctyne.
Mesoionic carbenes: Reactions of 1, 3-diphenyltetrazol-5-ylidene with electron-deficient alkenes, and synthesis and catalytic activities of the (tetrazol-5-ylidene)rhodium(I) complexes
Araki, Shuki,Yokoi, Keisaku,Sato, Ryosuke,Hirashita, Tsunehisa,Setsune, Jun-Ichiro
experimental part, p. 164 - 171 (2009/07/17)
The reactions of 1, 3-diphenyltetrazol-5-ylidene, a rare example of mesoionic carbenes, with electron- deficient unsaturated compounds were studied. The carbene reacted with dimethyl 1, 2, 4, 5-tetrazine-3, 6-dicarboxylate to give a 5-tetrazoliomethylide, together with hydrazine derivatives. The reaction with tetracyanoethylene gave another methylide in low yield. On the contrary, the reactions with weaker electrophiles, such as 3, 6-diphenyl-1, 2, 4, 5-tetrazine, fumalonitrile, N-phenylmaleimide, and dimethyl acetylenedicarboxylate, did not give any coupling products, but gave phenylated products and/or Michael addition products via the degradation of the 1, 3-diphenyltetrazole ring. Novel mesoionic mono- and bis(carbene)-rhodium(I) complexes were synthesized and the structures were characterized by X-ray crystallography. Their catalytic activities for the decarbonylative addition reaction of benzoyl chloride to ethynylbenzene were investigated.
N-benzyl DABCO tribromide - Promoted oxidative coupling of benzyl cyanides: A convenient procedure for the synthesis of α, α′- dicyanostilbenes
Matloubi Moghaddam, Firouz,Zargarani, Dordaneh,Boeini, Hassan Zali
, p. 1694 - 1702 (2008/09/20)
A convenient and efficient procedure was developed for preparing α,α′-icyanostilbenes through the oxidative coupling reaction of benzyl cyanide derivatives using N-benzyl DABCO tribromide as the oxidative bromination reagent in the presence of K2CO3 as a base. Copyright Taylor & Francis Group, LLC.
Stereoselective electrocatalytic oxidative coupling of phenylacetonitriles: Facile and convenient way to trans-α,β-dicyanostilbenes
Elinson, Michail N.,Dorofeev, Alexander S.,Feducovich, Sergey K.,Belyakov, Pavel A.,Nikishin, Gennady I.
, p. 3023 - 3027 (2008/03/12)
Electrolysis of phenylacetonitriles in methanol in an undivided cell in the presence of sodium halides as mediators induces a stereoselective oxidative coupling process that results in the formation of trans-α,β- dicyanostilbenes in 60-85% yield with 40-70% current efficiency. The application of this efficient stereoselective electrocatalytic method to the formation of trans-α,β-dicyanostilbenes represents an environmentally benign synthetic strategy and is valuable from the viewpoint of large-scale processes. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Expedient synthesis of glycidonitriles by darzens condensation of α-halogenonitriles with aldehydes and ketones
Jonczyk,Gadaj
, p. 1595 - 1610 (2008/09/17)
Chloroacetonitrile (1), α-halogenopropionitriles 4, and α-chlorophenylacetonitrile (6) react with aldehydes 2a,b,h-o and ketones 2c-g,p-t in the presence of solid NaOH in THF or DME, without any added catalyst, affording substituted glycidonitriles 3a-t, 5a, c-g,r,s and 7a,b,i,j,u,v, respectively (Darzens condensation). The glycidonitriles 3a-h, prepared from 1 and carbonyl compounds 2a-h, are obtained in high yields, exceeding those reported in the literature (Table 5). Expedient results of the reactions studied are due to increased reactivity of anions with Na+ as counterion in ethereal solvents. Investigation of the concentration of NaOH and the carbanion of diphenylacetonitrile in selected solvents reveals that ethereal solvents may increase the solubility of the anions participating in Darzens condensation.
Enediynes from aza-enediynes: C,N-dialkynyl imines undergo both aza-Bergman rearrangement and conversion to enediynes and fumaronitriles
Feng, Liping,Zhang, Aibin,Kerwin, Sean M.
, p. 1983 - 1986 (2007/10/03)
Aza-enediynes (C,N-dialkynyl imines) undergo thermal aza-Bergman rearrangement to β-alkynyl acrylonitriles through 2,5-didehydropyridine (2,5-ddp) intermediates. Certain aza-enediynes also undergo an alternative process affording enediynes and fumaronitri
Derivative of α,β-dicyanostilbene: Convenient precursor for the synthesis of diphenylmaleimide compounds, E-Z isomerization, crystal structure, and solid-state fluorescence
Yeh, Hsiu-Chih,Wu, Wei-Ching,Wen, Yuh-Sheng,Dai, De-Chang,Wang, Juen-Kai,Chen, Chin-Ti
, p. 6455 - 6462 (2007/10/03)
A convenient and efficient procedure was developed for preparing 3,4-diaryl-substituted maleimides through the improved synthesized diaryl-substituted fumaronitrile. The synthesis of diphenyl-substituted fumaronitrile derivatives from phenylacetonitrile compounds was analyzed and improved. We found the stoichiometry of the sodium methoxide and the concentration of the starting material, phenylacetonitrile derivatives, were crucial for the high yield and easy purification of the products. Particularly, bis(4-bromophenyl)fumaronitrile, bis(3-trifluoromethylphenyl)fumaronitrile, and bis(4-methoxyphenyl)fumaronitrile were isolated in good yields of 70-90% by simple suction filtration. In addition, 1H NMR provided compelling evidence that the E-Z isomerization was involved in the formation reaction of the maleimide compounds from either fumaronitrile or maleonitrile derivatives. Single-crystal X-ray structures of these three fumaronitrile derivatives, the first three of the kind, were obtained, revealing the nonplanar molecular structure. We ascribe the strong solid-state fluorescence of these diphenylfumaronitrile derivatives to the nonplanar structure that inhibits the close packing of the molecule aggregation and thus the fluorescence quenching.
Reaction of Hexachlorobenzene and (Pentachlorophenyl)lithium with α-Arylacetonitriles
Refat, Hala Mohammed,Waggenspack, John,Dutt, Mahesh,Zhang, Hongming,Fadda, A. A.,Biehl, Ed
, p. 1985 - 1989 (2007/10/02)
(Pentachlorophenyl)lithium (2) reacts with α-lithio-α-arylacetonitriles (4) at -70 deg C to room temperature to supply α-aryl-α-(2,3,5,6-tetrachlorophenyl)acetonitriles 7.Small amounts of 1,2,4,5-tetrachlorobenzene (8) and trans-1,2-dicyano-1,2-diarylethylenes 9 are also obtained; however, no α-tetrachloroarylated nitriles 6 from 3,4,5,6-terachlorobenzyne were detected.Similar treatment of hexachlorobenzene (1) and 4 afforded α-aryl-α-(2,3,4,5,6-pentachlorophenyl)acetonitriles 10.The addition of 2 to 4 at tetrachlorobenzyne-generating temperatures (0-20 deg C) gave a complex mixture containing mainly dimeric and polymeric materials; 6 was not found.A mechanism is proposed for the reaction of 2 and 4 which suggests that nitriles 7 are formed by the condensation of 2 and 4 via a four-centered transition state and that alkenes 9 are supplied by a base-mediated dimerization of α-chloro-α-arylacetonitriles 13, formed by a lithium-chlorine exchange between 2 and 4.Nitriles 10 most likely are provided from the reaction of 1 and 4 by the usual aromatic nucleophilic substitution pathway.
