14378-04-2Relevant academic research and scientific papers
One-pot Wittig reactions in aqueous media: A rapid and environmentally benign synthesis of α,β-unsaturated carboxylic esters and nitriles
Wu, Jinlong,Yue, Congyong
, p. 2939 - 2947 (2006)
One-pot Wittig reactions of ethyl bromoacetate and bromoacetonitrile with aldehydes in the presence of PPh3 and LiOH in water were investigated. Most of the olefination reactions completed within 5-120 min in refluxing water containing 1.2 M LiCl to afford the olefin products in 71-97% yields with 100:0-55:45 ratios of E:Z isomers. Copyright Taylor & Francis Group, LLC.
Polymer-assisted Horner-Emmons olefination using PASSflow reactors: pure products without purification.
Solodenko, Wladimir,Kunz, Ulrich,Jas, Gerhard,Kirschning, Andreas
, p. 1833 - 1835 (2002)
A PASSflow protocol for the Horner-Emmons olefination of aldehydes using polymer-bound hydroxide ions in flowthrough reactors is presented which allows preparation of alkenes in very high yield with minimal purification.
Stereoselective Synthesis of (E)-Cinnamonitriles with the SmI2/THF/MeOH System
Guo, Hongyun,Zhang, Yongmin
, p. 342 - 343 (1999)
α-Phenylsulfonylcinnamonitriles are readily reduced by SmI2/THF/MeOH to give the corresponding (E)-cinnamonitriles in good yields under mild conditions.
Substituted 3-phenylpropenoates and related analogs: Electron ionization mass spectral fragmentation and density functional theory calculations
Wheelock,Colvin,Sanborn,Hammock
, p. 1053 - 1062 (2008)
Analysis of ethyl 3-(2-chlorophenyl)propenoate by electron ionization mass spectrometry showed the distinct loss of an ortho chlorine. To characterize the structural requisites for the observed mass fragmentation, a series of 30 halogen-substituted 3-phenylpropenoate-related structures were examined. All ester-containing alkene derivatives exhibited loss of the distinctive chlorine from the 2-position of the phenyl ring. Analogous derivatives with the halogen (chlorine or bromine) in the para position did not evidence selective halogen loss. Results demonstrated that substituted 3-phenylpropenoates and their analogs fragment via the formation of a previously reported benzopyrylium intermediate. To understand the correlation between the intramolecular radical substitution and the abundance and selectivity of the chlorine (or other halogen) displacement, density functional theory calculations were performed to determine the charge on the principal cation involved in the chlorine loss (in the ortho, meta, and para positions), the charge for the neutral radical (noncation), the excess alpha-electron density on the relevant atom and the energy to form the cation from the neutral atom (ionization energy). Results showed that the selectivity and extent of halogen displacement correlated highly to the electrophilicity of the radical cation as well as the neutral radical. These data further support the proposed fragmentation mechanism involving intramolecular radical elimination. Copyright
Stereoselective synthesis of (E)-cinnamonitriles via heck arylation of acrylonitrile and aryl iodides in water
Zhao, Hong,Cai, Ming-Zhong,Peng, Chun-Yun
, p. 3419 - 3423 (2002)
Heck arylation of acrylonitrile and aryl iodides were carried out in the presence of catalytic amounts of Pd(OAc)2 and Bu4NBr in neat water and a variety of substituted (E)-cinnamonitriles were obtained in good yields under mild cond
Transmission of substituent effects through extended systems-I. p-Substituted cinnamonitriles
Butt, G.,Topsom, R. D.
, p. 811 - 818 (1980)
Infrared data, 13C chemical shifts and ab-initio calculations are reported for a series of p-substituted cinnamonitriles.The i.r. values include intensities for the benzene, ethylene and cyanide vibrations which allow an estimation of resonance effects.The relative importance of the various mechanisms of transmission of electronic effects are discussed.
Solid-phase synthesis of (E)-3-substituted acrylonitriles from polystyrene-supported α-selenoacetonitrile
Wang, Chao-Li,Huang, Yi-Xiang,Sheng, Shou-Ri,Yang, Wei,Cai, Ming-Zhong
, p. 1282 - 1289 (2009)
A facile method for solid-phase organic synthesis of (E)-3-substituted acrylonitriles in good yields using polystyrene-supported α- selenoacetonitrile has been developed. The advantages of this method include straightforward operation, lack of odor, good
Pd(II)-Catalyzed CC Bond Cleavage by a Formal Group-Exchange Reaction
Ye, Runyou,Zhu, Maoshuai,Yan, Xufei,Long, Yang,Xia, Ying,Zhou, Xiangge
, p. 8678 - 8683 (2021/07/26)
A chelation-assisted palladium-catalyzed CC bond cleavage of α, β-unsaturated ketone to form alkenyl nitrile in the presence of nitrile is disclosed on the basis of a formal group-exchange reaction formulated as C1C2 + C3 → C1C3 + C2, differing from normal alkene oxidative cleavage and metathesis type. The isolated key active Pd(II) complex as well as deuterium-labeled experiment revealed the necessity of the chelation group, and a plausible catalytic pathway was proposed.
Selective and facile synthesis of α,β-unsaturated nitriles and amides with N-hydroxyphthalimide as the nitrogen source
Yan, Yiyan,Xu, Xiaohe,Jie, Xiaokang,Cheng, Jingya,Bai, Renren,Shuai, Qi,Xie, Yuanyuan
supporting information, p. 2793 - 2796 (2018/06/25)
The direct conversion of α,β-unsaturated aldehydes to corresponding nitriles promoted by Pd(OAc)2 and phthalic acid which was hydrolyzed from N-hydroxyphthalimide (NHPI) has been disclosed. Additionally, it was found that when water was used as the solvent, α,β-unsaturated amides was obtained as the main products in good to excellent yields. It was first reported that NHPI was utilized as the nitrogen source to synthesize α,β-unsaturated nitriles and amides from aldehydes. Control experiment demonstrated that aldehydes undergo a process of oximation and dehydration to form nitriles and amides.
Synthesis of olefins via a Wittig reaction mediated by triphenylarsine
Li, Lun,Stimac, Jared C.,Geary, Laina M.
supporting information, p. 1379 - 1381 (2017/03/17)
An arsine-mediated Wittig reaction for the synthesis of olefins is described. After heating triphenylarsine in the presence of an activated alkyl bromide for 30?min, the resulting arsonium salt condensed with aldehydes in as little as 5?min at room temperature, yielding the olefins in high yields. Aromatic, heteroaromatic, and alkyl aldehydes were all suitable substrates for this process.
