2234-26-6Relevant academic research and scientific papers
Biomolecule-derived supported cobalt nanoparticles for hydrogenation of industrial olefins, natural oils and more in water
Pews-Davtyan, Anahit,Scharnagl, Florian Korbinian,Hertrich, Maximilian Franz,Kreyenschulte, Carsten,Bartling, Stephan,Lund, Henrik,Jackstell, Ralf,Beller, Matthias
supporting information, p. 5104 - 5112 (2019/09/30)
Catalytic hydrogenation of olefins using noble metal catalysts or pyrophoric RANEY nickel is of high importance in the chemical industry. From the point of view of green and sustainable chemistry, design and development of Earth-abundant, less toxic, and more environmentally friendly catalysts are highly desirable. Herein, we report the convenient preparation of active cobalt catalysts and their application in hydrogenations of a wide range of terminal and internal carbon-carbon double bonds in water under mild conditions. Catalysts are prepared on multi-gram scale by pyrolysis of cobalt acetate and uracil, guanine, adenine or l-tryptophan. The most active material Co-Ura/C-600 showed good productivity in industrially relevant hydrogenation of diisobutene to isooctane and in natural oil hardening.
Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile
Bhunia, Anup,Bergander, Klaus,Studer, Armido
supporting information, p. 16353 - 16359 (2018/11/25)
Catalytic transfer hydrocyanation represents a clean and safe alternative to hydrocyanation processes using toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile as a benign and readily available HCN source. A large set of nitrile derivatives (>50 examples) are prepared from both aliphatic and aromatic alkenes with good to excellent anti-Markovnikov selectivity. A range of aliphatic alkenes engage in selective hydrocyanation to provide the corresponding nitriles. The introduced method is useful for chain walking hydrocyanation of internal alkenes to afford terminal nitriles in good regioselectivities. This protocol is also applicable to late-stage modification of bioactive molecules.
MANUFACTURING METHOD OF NITRYL COMPOUND
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Paragraph 0027-0028; 0036, (2017/04/27)
PROBLEM TO BE SOLVED: To provide a method for manufacturing a nitryl compound at good efficiency and safety under a moderate reaction condition. SOLUTION: In a manufacturing method of a nitryl compound, an organic compound having a carbon-carbon unsaturated bond and acetone cyanhydrin are reacted in the presence of bivalent nickel compound, an organic phosphorus compound and a metal powder to add a nitryl group to one carbon constituting the carbon-carbon unsaturated bond. The metal powder is selected from zinc, magnesium, aluminum and manganese. The nickel compound is preferably halide salt of nickel, carboxylate of nickel and β-diketo compound salt of nickel. The organic phosphorus compound is preferably triphenylphosphine. The reaction between the organic compound and the acetone cyanhydrin can be conducted at a reaction temperature of 85°C to 90°C in a solvent of an alcohol compound. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
Unlocking Mizoroki–Heck-Type Reactions of Aryl Cyanides Using Transfer Hydrocyanation as a Turnover-Enabling Step
Fang, Xianjie,Yu, Peng,Prina Cerai, Gabriele,Morandi, Bill
supporting information, p. 15629 - 15633 (2016/10/24)
A new transfer hydrofunctionalization strategy to turnover H-MII-X complexes has enabled both intra- and intermolecular Mizoroki–Heck (MH)-type reactions of aryl cyanides that are challenging to realize under traditional, basic conditions. Initially, a cascade carbonickelation/MH reaction of 2-cyanostyrenes was achieved using a key alkyne transfer hydrocyanation step. Mechanistic experiments supported the proposed catalytic cycle, including the turnover-enabling transfer hydrocyanation step. The reactivity was then extended to the intermolecular MH reaction of benzonitriles and styrenes.
Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source
Nemoto, Koji,Nagafuchi, Tsuyoshi,Tominaga, Ken-ichi,Sato, Kazuhiko
, p. 3199 - 3203 (2016/07/06)
An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.
Synthetic studies related to diketopyrrolopyrrole (DPP) pigments. Part 1: The search for alkenyl-DPPs. Unsaturated nitriles in standard DPP syntheses: A novel cyclopenta[c]pyrrolone chromophore
Morton, Colin J.H,Gilmour, Ryan,Smith, David M,Lightfoot, Philip,Slawin, Alexandra M.Z,MacLean, Elizabeth J
, p. 5547 - 5565 (2007/10/03)
Reactions of the anion of ethyl 4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate with the Diels-Alder adducts of acrylonitrile and various dienes rarely yield the expected DPP derivatives. The reaction with cyclohex-3-enecarbonitrile provides a noteworthy exception: thermolysis of the resulting cyclohexenyl-DPP gives butadiene and impure 3-ethenyl-6-phenyl-DPP, the latter being thermally unstable. Michael additions predominate when the above anion reacts with α,β-unsaturated nitriles: acrylonitrile and methacrylonitrile give 4,4-bis(cyanoethyl) and 4,4-bis(2-cyanopropyl) derivatives, and cinnamonitrile, substituted cinnamonitriles and 3-(2-thienyl)acrylonitrile give deep red 3-aryl-5-cyano-4-hydroxy-2H-cyclopenta[c]pyrrol-1-ones. These ambident nucleophiles may undergo N- and either O- or C-alkylation according to the alkylating agent used.
Azide and Cyanide Displacements via Hypervalent Silicate Intermediates
Soli, Eric D.,Manoso, Amy S.,Patterson, Michael C.,DeShong, Philip,Favor, David A.,Hirschmann, Ralph,Smith III, Amos B.
, p. 3171 - 3177 (2007/10/03)
Hypervalent azido- and cyanosilicate derivatives, prepared in situ by the reaction of trimethylsilyl azide or trimethylsilyl cyanide, respectively, with tetrabutylammonium fluoride, are effective sources of nucleophilic azide or cyanide. Primary and secondary alkyl halides and sulfonates undergo rapid and efficient azide or cyanide displacement in the absence of phase transfer catalysts with the silicate derivatives. Application of these reagents to the stereoselective synthesis of glycosyl azide derivatives is reported.
The synthesis of 2-cyclohexylideneperhydro-4,7-methanoindenes. Non-steroidal analogues of steroidal GABAA receptor modulators
Burden, Peter M.,Allan, Robin D.,Hambley, Trevor,Johnston, Graham A. R.
, p. 3163 - 3169 (2007/10/03)
Racemic (3aα,4β,7β,7aα)-2-cyclohexylideneperhydro-4,7- methanoindene derivatives (±)-3 and (±)-4 were synthesised as analogues of steroidal GABAA receptor modulators 1 and 2 respectively. The lithium dianion generated from epimeric 2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene-2-carboxylic acids, 8 and 9, reacted with a commercially available cyclohexanone to generate β-hydroxy carboxylic acids. Cyclodehydration to β-lactones followed by the thermal elimination of carbon dioxide gave a suitably functionalised 2-cyclohexylidenehexahydro-4,7-methano-1H-indene derivative 18. Regio- and stereospecific hydrocyanation of the bicyclo[2.2.1]hept-2-ene moiety of 18 was achieved via hydroboration affording a racemic nitrile, 19. This underwent further transformations to give (±)-3 and (±)-4 and their hydroxy group epimers (±)-5 and (±)-6 respectively. X-Ray structure data was obtained for (±)-3. The effects of compounds (±)-3-(±)-6 on the binding of the GABAA receptor agonist [3H]muscimol to rat synaptic membranes were measured. Compound (±)-4 was a weak positive modulator while the others were inactive.
2-Substituted histamines with G-protein-stimulatory activity
Detert, H.,Hagelueken, A.,Seifert, R.,Schunack, W.
, p. 271 - 276 (2007/10/02)
The cationic-amphiphilic 2-substituted histamines, 2-(2-chlorophenyl)histamine (2-ethanamine) and 2-(2-cyclohexylethyl)histamine, activate pertussis toxin-sensitive guanine nucleotide-binding proteins (G-proteins) of the Gi-subfamily by a receptor-independent mechanism.We studied structure-activity relationships of 2-substituted histamine derivatives for this G-protein activation using six known and 12 newly synthesized compounds.Elongation of the alkyl chain between imidazole and the ring system enhanced the potency and efficiency of substances in activating high-affinity GTP hydrolysis, ie the enzymatic activity of G-protein α subunits, in membranes of HL-60 leukemic cells.Cyclopentyl-, cyclohexyl- and norbornyl-substituted histamines were more effective and potent than phenyl-substituted histamines in mediating G-protein activation in HL-60 membranes and in activating reconstituted bovine brain Gi/Go-proteins.Our data show that the chain length and the type of ring system are important determinants for receptor-independent G-protein activation by 2-substituted histamines.With respect to histamine H1-receptors, most of the substances studied displayed weak antagonistic activity.
