15016-11-2Relevant academic research and scientific papers
STEREOSELECTIVE SYNTHESIS OF CIS-2,3-DIPHENYL-2-CYANOOXIRANE BY REACTION OF 2-BROMODEOXYBENZOIN WITH CYANIDE ION ON SOLID ADSORBENTS
Takahashi, Kazumasa,Nishizuka, Toshio,Iida, Hirotada
, p. 2389 - 2390 (1981)
Treatment of 2-bromodeoxybenzoin with cyanide ion in the presence of solid adsorbent (silica gel or alumina) stereoselectively gives cis-2,3-diphenyl-2-cyanooxirane in a good yield.The mechanism is discussed.
Stereoselective Syntheses of cis-Cyanooxiranes by Reaction of α-Bromoketones with Cyanide Ion Adsorbed onto Hemin-Copolymer
Saito, Kiyoshi,Harada, Kaoru
, p. 1651 - 1654 (1989)
Sterically controlled addition reactions of cyanide to α-bromoketones by using CN-modified hemin copolymer in nonaqueous system were carried out, and cis-cyano-oxiranes were obtained selectively.
BF3·OEt2-mediated [1,2]-aryl shift: Synthesis of functionalized α-arylnitriles via the bromination/cyanation/deformylation of substituted deoxybenzoin
Chan, Chieh-Kai,Chang, Meng-Yang
, p. 5207 - 5213 (2017/07/28)
A new sequential, tandem synthesis of functionalized α-arylnitriles via the bromination/cyanation/deformylation of substituted deoxybenzoin has developed. CuBr2-promoted bromination of substituted deoxybenzoins gives 2-bromo-2-arylacetophenne 3. The cyanation of 3 with sodium cyanide (NaCN) generates epoxynitrile. Then, a treatment of epoxynitrile with BF3·OEt2 results in the formation of functionalized α-arylnitriles 4 via a 1,2-aryl shift.
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.
Convenient method for epoxidation of alkenes using aqueous hydrogen peroxide
Man, Kin Tse,Klawonn, Markus,Bhor, Santosh,Doebler, Christian,Anilkumar, Gopinathan,Hugl, Herbert,Maegerlein, Wolfgang,Beller, Matthias
, p. 987 - 990 (2007/10/03)
(Chemical Equation Presented) The complex [Ru(tpy)(pydic)] (1a) is an active catalyst for epoxidation of alkenes by aqueous 30% hydrogen peroxide in tertiary alcohols. The protocol is simple to operate and gives the corresponding epoxides in good to excellent yields. Chiral enantiopure [Ru(tpy*)(pydic) ] complexes have been synthesized and successfully applied in this procedure.
Generation and reaction of ammonium ylides in basic two-phase systems
Kowalkowska, Anna,Sucholbiak, Dorota,Jonczyk, Andrzej
, p. 925 - 933 (2007/10/03)
Reaction of the quaternary ammonium salts 2a-i with electrophilic alkenes 3, active alkylating agents 7 or aromatic aldehydes 11, carried out in basic two-phase systems A-D, afforded cyclopropanes 4, cyanoalkenes 8 or cyanooxiranes 12 respectively, via the corresponding ammonium ylides 2+-. The method is very simple, and gives cyclopropanes 4 and cyanoalkenes 8 in high yield. Under similar conditions, 1-cyanodienes 8aa,ba were cyclopropanated at the γ,δ-double bond with formation of vinylcyclopropanes 9a,b. The stereochemistry of the prepared cyclopropanes was elucidated from literature, 1H NMR spectroscopic data, NOE experiments or X-ray single crystal analysis. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Generation and reactions of ammonium ylides in basic two-phase systems: Convenient synthesis of cyclopropanes, oxiranes and alkenes substituted with electron-withdrawing groups
Jończyk, Andrzej,Konarska, Anna
, p. 1085 - 1087 (2007/10/03)
Quaternary ammonium salts 1 react with electrophilic alkenes 2, aromatic aldehydes 3 and alkylating agents 4, in the presence of 50% aq sodium hydroxide or powdered potassium carbonate, in dichloromethane, to form cyclopropanes 5, oxiranes 6 and alkenes 7
Electrolytic Oxidation of Ketones in a Methanolic Solution of NaCN in the Presence of Catalytic Amounts of KI
Okimoto, Mitsuhiro,Chiba, Toshiro
, p. 6194 - 6197 (2007/10/02)
The indirect electrolytic oxidation of ketones (1) in methanolic sodium cyanide was studied using iodide ion as a mediator.The product and the reactivity of ketone were dependent on the nature of the alkyl groups attached to the carbonyl group.Thus, 2-alk
Fluoride-promoted Epoxidation of α,β-Unsaturated Compounds
Miyashita, Masaaki,Suzuki, Toshio,Yoshikoshi, Akira
, p. 285 - 288 (2007/10/02)
The epoxidation of α,β-unsaturated compounds using tetrabutylammonium fluoride is described.This method has been demonstrated to be directly applicable to base-sensitive substrates such as cinnamaldehyde and α-phenylcinnamonitrile.
Reactions of Carbanions with Carbon Tetrachloride in Two-Phase Systems. Chlorinated Products as Nucleophilic and Electrophilic Intermediates
Makosza, M.,Kwast, A.,Kwast, E.,Jonczyk, A.
, p. 3722 - 3727 (2007/10/02)
A variety of carbanions generated in the catalytic two-phase system (aqueous NaOH or K2CO3 and tetrabutylammonium bromide catalyst) react with CCl4 to form chlorinated products that can react as nucleophiles and electrophiles.Thus, chlorinated intermediates generated from arylacetonitriles and propiophenone in the presence of aldehydes and electrophilic alkenes form oxirane and cyclopropane derivatives, respectively.The chlorinated intermediates act as electrophiles toward Cl3C- giving (trichloromethyl)oxiranes (from aryl alkyl ketones), α-trichloromethyl nitriles (from phenyl(dialkylamino)acetonitriles), and benzoyldichloro enamines (from α-dialkylamino ketones).From secondary nitroalkanes both chloronitroalkanes and dinitro compounds can be produced.
