4786-20-3Relevant academic research and scientific papers
C-CN BOND CLEAVAGE UNDER MILD CONDITIONS PROMOTED BY ELECTRON-RICH COBALT COMPLEXES
Ozawa, Fumiyuki,Iri, Kiyoshi,Yamamoto, Akio
, p. 1707 - 1710 (1982)
Electron-rich cobaltate dinitrogen complex, Li(Et2O)3 1, reacts with alkyl and aryl nitrile compounds causing the cleavage of C-CN bond under mild conditions to release hydrocarbons.Catalytic activity of the cobalt complex to isomerize allyl cyanide to crotononitrile is also noted.
Base-Catalyzed Isomerization of 3-Butenenitrile. Relative Nucleophilicities of Carbanions, Nitranions, Oxanions, and Thianions toward Hydrogen
Bordwell, Frederick G.,Hughes, David L.
, p. 4737 - 4744 (1985)
Rate constants for base-catalyzed isomerization of CH2=CHCH2CN to CH3CH=CHCN in Me2SO solution by families of carbanions (C(1-)), nitranions (N(1-)), oxanions (O(1-)), and thianions (S(1-)) have been measured.The relative catalytic effect of these anions at the same basicity is S(1-), O(1-) > N(1-) > C(1-).This order is the same as that observed previously for attack of families of anions of these types on a β-hydrogen atom in elimination reactions from cyclohexyl bromide, but it differs from that for attack on carbon in SN2 reactions: S(1-) >> C(1-) > O(1-) > N(1-).The Broensted coefficients, wich measure the sensitivity of the rates to changes in basicity, were in the range 0.8-1.These large values are consistent with previous values determined for deprotonation of α-CN carbon acids, but not with the predictions of the Leffler-Grunwald rate-equilibrium equation.A review of the literature failed to provide support for the Leffler-Grunwald postulate that β will approach zero for exergonic proton transfers from carbon acids and unity for endergonic proton transfers.The results are rationalized by a two-step mechanism for proton transfers involving a hydrogen-bonded carbanion intermediate.The failure of substituent effects on protonations of carbanions to conform to those observed in the deprotonation of the corresponding carbon acids provides evidence against a one-step mechanism.Our observations argue against the application of the Hammond-Leffler postulate to most organic reactions over the usual reactivity ranges studied.
Base controlled diverse reactivity of allyl cyanide for synthesis of multi-substituted benzenes
Yadav, Pratik,Shaw, Ranjay,Elagamy, Amr,Kumar, Abhinav,Pratap, Ramendra
, p. 5465 - 5473 (2018)
A base controlled regioselective 1,6-cyanoallylation of suitably functionalized 2H-pyran-2-ones has been demonstrated for the synthesis of various multi-substituted benzenes through a tandem process. We observed that lithium hydroxide provides a major product from α-attack and a minor product from γ-attack of allyl cyanide, while the use of sodium hydride as a base exclusively provides the product by γ-attack of allyl cyanide. We have also performed NMR experiments to understand the mechanistic pathway. The structure of the compound was confirmed by single crystal X-ray analysis.
Spectra of carbanions formed from ally1 cyanide during isomerization in zeolite Nay-FAU with strong basic sites
Hannus, Istvan,Foerster, Horst,Tasi, Gyula,Kiricsi, Imre,Molnar, Arpad
, p. 345 - 348 (1995)
Double bond isomerization of ally1 cyanide to crotononitrile over a basic zeolite catalyst was monitored by IR and UV-VIS spectroscopy in order to get information on the surface intermediates involved. Due to the spectral changes the occurence of a carbanionic intermediate seems to be highly probable characterized by an absorption at 400 nm.
Relative Donor-Atom Effects on Rates of Isomerization of 3-Butenenitrile Catalyzed by Anions of the Same Basicity
Bordwell, Frederick G.,Hughes, David L.
, p. 619 - 621 (1983)
For base-catalyzed isomerization of 3-butenenitrile in Me2SO solution the order of rate constants for anions of the same basicity is ArS->ArO->RSO2NAr->9-G-Fl- (9-substituted fluorenyl carbanions).The relative rate constants vary somewhat with basicity since the Broensted β values are 0.77, 1.0, 0.82, and ca. 0.8, respectively.
LJ reaction in the preparation wittich reagent and application of glufosinate in
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Paragraph 0094; 0095, (2017/12/04)
The present invention relates to an application of a new LJ intramolecular isomerization reaction in preparation of a wittig reagent and a herbicide of glufosinate-ammonium. With the application, a new approach of a synthesis route for preparing the wittig reagent and the glufosinate-ammonium is developed, the disadvantages of the existing wittig reaction are improved, and the industrial design of the glufosinate-ammonium production is improved.
Unusual reactivity of N-tert-butylimines under FVT conditions
Le?niak, Stanis?aw,Pasternak, Beata,Justyna, Katarzyna,Vu, Thien Y.,Huynh, Thi Kieu Xuan,Khayar, Sa?d,Dargelos, Alain,Chrostowska, Anna
, p. 722 - 729 (2013/07/27)
Thermal reactions of N-tert-butyl-(E)-crotonaldimine (1a) and 1,4-di-(tert-butyl)-1,4-diazabuta-1,3-dien (glyoxal-bis-N-tert-butylimine) (1b) under FVT conditions have been studied. It has been found that at 800 °C compound 1a yielded pyrrole and crotonon
New tetraphosphorus ligands for highly linear selective hydroformylation of allyl and vinyl derivatives
Cai, Chaoxian,Yu, Shichao,Cao, Bonan,Zhang, Xumu
experimental part, p. 9992 - 9998 (2012/09/07)
New tetraphosphorus ligands have been developed and applied in the rhodium-catalyzed regioselective hydroformylation of a variety of functionalized allyl and vinyl derivatives. Remarkably high linear selectivity was obtained by these tetraphosphorus ligands. The ligand that bears strong electron-withdrawing 2,4-difluorophenyl groups is the most effective one in affording linear aldehydes. The Rh/tetraphosphorus ligand catalyst is highly effective to produce linear aldehydes from functionalized allyl derivatives with heteroatoms or aromatic groups directly adjacent to the allyl group. For vinyl derivatives, the ligand is highly linear selective for acrylic derivatives, styrene, vinyl pyridine, and vinyl phthalimide. Linear to branch ratios of 26:1 and 10:1 were obtained for the hydroformylation of styrene and allyl cyanide, respectively. New tetraphosphorus ligands have been developed and applied in the rhodium-catalyzed regioselective hydroformylation of a variety of allyl and vinyl olefins (see scheme). Remarkably high linear selectivities were obtained by these ligands. Linear-to-branch ratios of 26:1 and 10:1 were obtained for the hydroformylation of styrene and allyl cyanide, respectively. Copyright
CONTROLLED DRUG RELEASE FROM SOLID SUPPORTS
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Page/Page column 31-32, (2011/11/30)
The invention relates to solid supports useful in medical applications that provide controlled release of drugs, such as peptides, nucleic acids and small molecules. The drugs are covalently coupled to the solid support through a linkage that releases the drug or a prodrug through controlled beta elimination.
CONTROLLED RELEASE FROM MACROMOLECULAR CONJUGATES
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Page/Page column 24-25, (2011/11/30)
The invention relates to conjugates of macromolecular carriers and drugs comprising linkers that release the drug or a prodrug through rate-controlled beta-elimination, and methods of making and using the conjugates.
