Novel Ring Closure Carbonylation Reaction of 1,5-Cyclooctadiene in the Presence of Pd(II)-Catalysts

1992 ◽  
Vol 57 (11) ◽  
pp. 2374-2382 ◽  
Author(s):  
Curtis B. Anderson ◽  
Rade Marković
Keyword(s):  
Carbon Monoxide ◽  
Double Bond ◽  
Methylene Chloride ◽  
Ring Closure ◽  
Oxidative Carbonylation ◽  
Experimental Conditions ◽  
Carbonylation Reaction ◽  
Methanol Mixture

Oxidative carbonylation of 1,5-cyclooctadiene in methylene chloride-methanol mixture, catalyzed by Pd(II)-salts, gave rise to a bicyclic, bifunctional product under mild experimental conditions. The mechanism, involving multiple carbon monoxide and double bond insertions into the Pd(II)-carbon σ-bond, has been proposed, as being consistent with the outcome of this novel ring closure reaction.

Palladium-catalyzed carbonylation of 1,5-cyclooctadiene. Effects of temperature and pressure

1991 ◽  
Vol 56 (3) ◽  
pp. 663-672 ◽  
Author(s):  
Curtis B. Anderson ◽  
Rade Marković
Keyword(s):  
Carbon Monoxide ◽  
Oxidative Carbonylation ◽  
Influence Of Temperature ◽  
Carbonylation Reaction ◽  
Palladium Catalyzed ◽  
Effects Of Temperature ◽  
Temperature And Pressure

The influence of temperature and carbon monoxide pressure on the course of oxidative carbonylation reaction of 1,5-cyclooctadiene in the presence of the palladium(II) salts as a catalyst, was investigated.

scholarly journals Catalyst Initiation in the Oscillatory Carbonylation Reaction

2011 ◽  
Vol 2011 ◽  
pp. 1-11 ◽  
Author(s):  
Katarina Novakovic ◽  
Julie Parker
Keyword(s):  
Carbon Monoxide ◽  
Chemical Reactions ◽  
Potassium Iodide ◽  
Significant Role ◽  
Reaction Network ◽  
Oxidative Carbonylation ◽  
Heat Of Reaction ◽  
Oscillatory Reaction ◽  
Oscillatory Behaviour ◽  
Carbonylation Reaction

Palladium(II) iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II) iodide within this oscillatory reaction. The species researched include methanol, palladium(II) iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

Palladium-catalyzed oxidative carbonylation of hydrazides: synthesis of 1,3,4-oxadiazol-2(3H)-ones

2015 ◽  
Vol 51 (10) ◽  
pp. 1905-1907 ◽  
Author(s):  
Yu Wang ◽  
Xu Meng ◽  
Yuting Yang ◽  
Lutao Zhang ◽  
Shuaibo Guo ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Carbonyl Group ◽  
Intramolecular Cyclization ◽  
Oxidative Carbonylation ◽  
Amine Group ◽  
Mild Conditions ◽  
Carbonylation Reaction ◽  
Efficient Access ◽  
Wide Range ◽  
Palladium Catalyzed

A novel palladium-catalyzed oxidative carbonylation reaction was developed via the carbon monoxide insertions between the amine group and the carbonyl group to realize the intramolecular cyclization, which provides efficient access to 1,3,4-oxadiazol-2(3H)-ones with a wide range of substrates under mild conditions, resulting in good to excellent yields.

The addition of 2,4-dinitrobenzenesulphenyl chloride to 1,3-disubstituted allenes: a reexamination

1979 ◽  
Vol 57 (1) ◽  
pp. 119-127 ◽  
Author(s):  
Dennis G. Garratt ◽  
Pierre Beaulieu
Keyword(s):  
Double Bond ◽  
Chloride Solution ◽  
Methylene Chloride ◽  
Effective Mechanism ◽  
Substituent Group ◽  
Methylene Chloride Solution ◽  
Inductive Effects ◽  
Allene System

The reaction of 2,4-dinitrobenzenesulphenyl chloride with eight alkyl 1,3-disubstituted allenes in methylene chloride solution has been investigated. In contrast to earlier reports, attack by sulphur is found to occur exclusively at the central allenic carbon. The direction of approach of sulphenyl chloride leads preferentially to the formation of the E isomers in accord with the concept of steric approach control. The ratio of E to Z alkene is found to increase as the bulk of the substituent group cis to the arylthio group increases. We observe, however, very little regioselectivity with respect to which of the mutually perpendicular π bonds of the allene system is attacked, suggesting the presence of an effective mechanism for transmission of inductive effects to the more distant double bond.

Reductive Activation of Carbon Tetrachloride by Human Haemoglobin

1993 ◽  
Vol 21 (1) ◽  
pp. 57-64
Author(s):  
Roberta Ferrara ◽  
Michela Rezzadore ◽  
Stefano Cazzaro ◽  
Roberto Tolando ◽  
Maurizio Manno
Keyword(s):  
Carbon Monoxide ◽  
Carbon Tetrachloride ◽  
Anaerobic Incubation ◽  
Reductive Activation ◽  
Anaerobic Conditions ◽  
Prosthetic Group ◽  
Experimental Conditions ◽  
Human Haemoglobin ◽  
Reductive Metabolism

The reductive metabolism of carbon tetrachloride (CC14) by human haemoglobin (Hb) was observed in vitro by absolute absorption spectra recorded under anaerobic conditions. The following results were obtained: 1) a decrease of the 430nm peak typical of free reduced Hb (Hb2+); 2) the formation of a shoulder of absorbance, attributable to the production of a complex between Hb2+ and a metabolite of CC14 carbon monoxide (Hb-CO); and 3) the oxidation of some Hb2+ to methaemoglobin (Hb3+). The concentration of these three forms — Hb2+, Hb-CO and Hb3+ — during anaerobic incubation of Hb with CC14 was calculated algebraically from the absolute spectra. CO production was then calculated from the concentration of Hb-CO, using a suitable calibration curve. Interestingly, under identical experimental conditions, a substrate-dependent loss of Hb-derived haem, but not of Hb itself nor of haem-derived porphyrin fluorescence, was measured. Preliminary HPLC studies to clarify the discrepancy and, in particular, the role and fate of the haem group, showed two substrate-dependent modified haem products. The results indicate that human Hb is able to catalyse the reductive activation of CCl4, and suggest that, during the process, its prosthetic group haem may be modified by CC14 metabolites to products which maintain a tetrapyrrolic structure but are unable to react with pyridine.

scholarly journals Evaluations about the physico-chemical stability of docetaxel and irinotecan pre-diluted and diluted solutions: pharmaco-economic perspectives

2013 ◽  
Vol 3 (1) ◽  
pp. 6 ◽  
Author(s):  
Mariarita Laforgia ◽  
Anna Elisa Quatrale ◽  
Nicola A. Colabufo ◽  
Amalia Azzariti ◽  
Angelo Paradiso ◽  
...  
Keyword(s):  
Chemical Stability ◽  
Mobile Phase ◽  
Ammonium Acetate ◽  
Physical Stability ◽  
Experimental Conditions ◽  
Phase Gradient ◽  
Methanol Mixture ◽  
Physico Chemical ◽  
Starting Point ◽  
Economic Perspectives

Several clinically used anticancer drugs are well-known as far as their pharmacologic properties are concerned, but scarcely ever the interest towards their physico-chemical characteristics in solution led to practical acknowledgement in their management. Thanks to the Units for Centralized Anticancer Drug Handling, the importance to evaluate the concentration of saturation (physical stability) or the possible transformations undergone by a drug in solution (chemical stability) has become the starting point for avoiding useless wasting drugs and economic resources. By HPLC experiments we have demonstrated that the solutions of two drugs, docetaxel and irinotecan, are particularly stable at different concentrations and times of analyses in our experimental conditions. The best mobile phase for docetaxel was water/methanol/acetonitrile in 42/32/26 volumetric ratio: for halving concentrations (0.72-0.36-0.18-0.09 mg/mL) in NaCl 0.9%, the highest value gave a six-day and the three lower concentrations a fourteen-day stability, when storage occurred at room temperature and light protected. Elution of irinotecan was possible through an analysis in mobile phase gradient: at t0 a 20% ammonium acetate 10 mM and 80% methanol mixture, and after 5 min, a 80% ammonium acetate 10 mM and 20% methanol mixture. The physico-chemical stability was showed for five days, for any concentration of analysis when storage occurred at 2-8°C and light protected.

Carbon monoxide determinations in postmortem tissues as an aid in determining physiologic status prior to death

1959 ◽  
Vol 14 (3) ◽  
pp. 313-320 ◽  
Author(s):  
Syrrel S. Wilks ◽  
Robert T. Clark
Keyword(s):  
Experimental Data ◽  
Carbon Monoxide ◽  
Human Beings ◽  
Controlled Experiments ◽  
Experimental Conditions ◽  
Aircraft Accidents ◽  
Solid Tissue ◽  
Solid Tissues ◽  
Tissue Specimens ◽  
Aircraft Crash

With appropriate methodology, carbon monoxide in the ‘solid’ tissues of animals was quantitated and correlated with the blood carbon monoxide level in a series of controlled experiments with rats and dogs. Experimental conditions simulating aircraft crashes were devised and again the blood and ‘solid’ tissue CO levels were determined. Using the experimental data on animals as a basis for extrapolating blood CO levels, along with tissue CO values, obtained from ‘control’ and CO-asphyxial cases in human beings, an analysis was made of the ‘solid’ tissue specimens obtained in 186 fatal aircraft accidents. From the analysis of tissue specimens from approximately 200 aircraft crash cases, some 30% gave by this method a blood CO level in excess of 30% saturation. These results point to the likelihood that CO was present in the personnel compartments of some or all of these aircraft at some time during flight. Submitted on September 22, 1958

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