Carbonyl ylides and carbenes from thermolysis of oxadiazolines. Substituent effects on intramolecular and intermolecular reactions of carbonyl ylides

1983 ◽  
Vol 61 (3) ◽  
pp. 619-624 ◽  
Author(s):  
Michel Békhazi ◽  
John Warkentin
Keyword(s):  
Lower Limit ◽  
Rate Constant ◽  
Rate Constants ◽  
Carbonyl Compounds ◽  
Substituent Effects ◽  
Similar Rate ◽  
The Other ◽  
Competitive Process ◽  
Carbonyl Ylide ◽  
Intermolecular Reactions

Thermolysis of a 2-methoxy-Δ3-1,3,4-oxadiazoline involves loss of N2 with formation of a carbonyl ylide. The fate of the carbonyl ylide depends on its environment and on the other substituents present. Thus, the ylides from 2-methoxy-2,5,5-trimethyl-Δ3-1,3,4-oxadiazoline (1) and from 2-methoxy-2-(4-methoxyphenyl)-5,5-dimethyl-Δ3-1,3,4-oxadiazoline (2) are trapped very efficiently by methanol. However, the ylide from 1 is trapped much less efficiently than that from 2 by dimethylacetylene dicarboxylate, cis-1,2-dichloroethylene, or norbornadiene. A major competitive process in the case of 1 is fragmentation of the ylide to carbonyl compounds and carbenes, the latter being trapped by alkenes to form cyclopropanes. An intramolecular 1,4-H transfer is also competitive under some conditions. The ylide from 2 does not appear to fragment, nor does it undergo the 1,4-H transfer, but it cyclizes efficiently to the oxirane in the absence of trapping agents.Preliminary estimates of rate constants for cyclization of the ylide from 2 to form the oxirane [Formula: see text] and for its additions to norbornadiene and to dimethylacetylene dicarboxylate (1 × 105 M−1 s−1 and 1 × 109 M−1 s−1, respectively) are reported. If it is assumed that the ylide from 1 would add to dimethylacetylene dicarboxylate with a similar rate constant, then the yield for that process can be used to place a lower limit of 1010 s−1 on the rate constant for fragmentation of that ylide at 31 °C.

Substituent effects of rate constants for thermal [4π + 2π] cycloreversion of spiro-fused β-lactam oxadiazolines

1993 ◽  
Vol 71 (6) ◽  
pp. 907-911 ◽  
Author(s):  
Michel Zoghbi ◽  
John Warkentin
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Rate Constants ◽  
Transition States ◽  
Substituent Effects ◽  
Ground States ◽  
Phenyl Substituent ◽  
First Order ◽  
Average Value ◽  
Carbonyl Ylide

Twelve Δ3-1,3,4-oxadiazolines in which C-2 is also C-4 of a β-lactam moiety (spiro-fused β-lactam oxadiazoline system) were thermolyzed as solutions in benzene. Substituents in the β-lactam portion affect the rate constant for thermal decomposition of the oxadiazolines to N2, acetone, and a β-lactam-4-ylidene. The total spread of first-order rate constants at 100 °C was 47-fold and the average value was 6.7 × 10−4 s−1. A phenyl substituent at N-1 or at C-3 was found to be rate enhancing, relative to methyl. At C-3, H and Cl were also rate enhancing, relative to methyl. The data are interpreted in terms of the differential effects of substituents on the stabilities of the ground states, and on the stabilities of corresponding transition states for concerted, suprafacial, [4π + 2π] cycloreversion. The first products, presumably formed irreversibly, are N2 and a carbonyl ylide. The latter subsequently fragments to form acetone (quantitative) and a β-lactam-4-ylidene.

Substituent effects on rates of formation of methoxy-substituted carbonyl ylides from 2-aryl-2-methoxy- and 5-aryl-2-methoxy-Δ3-1,3,4-oxadiazolines

1984 ◽  
Vol 62 (8) ◽  
pp. 1646-1652 ◽  
Author(s):  
Michel Békhazi ◽  
Peter J. Smith ◽  
John Warkentin
Keyword(s):  
Transition State ◽  
Electron Density ◽  
Rate Constants ◽  
Substituent Effects ◽  
Partial Identification ◽  
Trans Isomers ◽  
First Order Kinetics ◽  
Bond Scission ◽  
Carbonyl Ylide ◽  
Substituent Constants

2-Aryl-2-methoxy-5,5-dimethyl-Δ3-1,3,4-oxadiazolines (4) and 5-aryl-2-methoxy-2,5-dimethyl-Δ3-1,3,4-oxadiazolines (5) were synthesized. Compounds 4 decompose in solution with first order kinetics. Rate constants are correlated with Hammett substituent constants (σ−) with ρ(49.2 °C) = 0.74 and 0.89 for CCl4, and CD3OD, respectively. The final products from 4 indicate that thermolysis involves the cleavage of both C—N bonds, to form N2 and, initially, a carbonyl ylide. Compounds 5, which were obtained as mixtures of cis/trans isomers containing several impurities, and which therefore gave poorer kinetic data, decomposed in CDCl3 solution with [Formula: see text] Carbonyl ylide intermediates, similar to those from the closelyrelated compounds 4, were assumed on the basis of analogy and on the basis of partial identification of products. The effects of para substituents in the aryl groups of 4 and 5 show that the transition states have greater electron density at C-2 of 4 and at C-5 of 5 than do the starting materials. In spite of the increase in electron density at C-2 of 4, the transition state must be less polar, overall, than the ground state because rate constants for thermolysis of 4 in methanol are smaller than those for CCl4, solvent. A plausible explanation for the substituent effects and the solvent effects is that the loss of N2 is concerted, with a transition state resembling more closely a spin paired 1,3-diradical than a 1,3-dipole. Alternative stepwise mechanisms, in which C2—N3 bond scission of 4 and C5—N4 bond scission of 5 are the rate-determining steps, leading to 1,5-diradical intermediates, can not be excluded on the basis of the evidence.

The Rate-Constant for the Recombination of Methyl Radicals

1986 ◽  
Vol 39 (8) ◽  
pp. 1257 ◽  
Author(s):  
NL Arthur ◽  
JC Biordi
Keyword(s):  
Experimental Data ◽  
High Pressure ◽  
Rate Constant ◽  
Rate Constants ◽  
The Other ◽  
Methyl Radicals ◽  
Experimental Conditions ◽  
Temperature Range ◽  
Best Value ◽  
Limiting Value

Rate constants for the recombination of CH3 radicals have been measured by means of the rotating sector technique in the temperature range 373- 463 K, and at a pressure of 30 Torr . CH3 radicals were produced by the photolysis of acetone, and the experimental data were fitted to sector curves generated from Shepp's theory. The results give kb = (2.81�0.22)×1013 cm3 mol-1 s-1, which, under the chosen experimental conditions, is close to its high-pressure limiting value. A comparison is made with the other values of the rate constant reported in the literature, and a best value is suggested.

Kinetics of renin-antirenin reaction: micromethods for the assay of renin and antirenin

1975 ◽  
Vol 228 (4) ◽  
pp. 973-979 ◽  
Author(s):  
E Haas ◽  
H Goldblatt ◽  
RL Klick ◽  
L Lewis
Keyword(s):  
Experimental Data ◽  
Lower Limit ◽  
Rate Constant ◽  
Rate Constants ◽  
Data Accuracy ◽  
Michaelis Constant ◽  
Renin Substrate ◽  
Method Of Calculation ◽  
Human Renin ◽  
Kinetics Of

Indirect micromethods were designed for the assay of human renin (lower limit 0.25 times 10-4 U and of antirenin to human renin (lower limit 3 times 10-4 U), with the rat used for the bioassay of the angiotensin produced by the action of renin on renin substrate. This made possible the assay of unusually small amounts (0.01 mu1) of serum for antirenin. The Michaelis-Menten concept of a dissociating complex can be applied to the antireninrenin reaction: the rate constants for the formation and for the breakdown of the complex were k1 equal to 1.65 (ml/U antirenin per min) and k3 equal to 1.97 times 10-3 (U inactivated renin/U antirenin per min), respectively; the apparent Michaelis constant was 12 times 10-4 (U renin/ml). A second method of analysis was also applied by assuming the formation of a rather tight complex, with antirenin functioning as an irreversible inactivator of renin. Both methods of analysis yielded practically the same rate constant (k1 equal to 1.65 and k1 equal to 1.71), but the treatment according to the Michaelis-Menten equation affords a slightly better fit of the experimental data (accuracy equal to plus or minus 15.5 percent) than the second method of calculation (accuracy equal to plus or minus 21.6 percent).

scholarly journals Hyperoxidation of Peroxiredoxins 2 and 3

2013 ◽  
Vol 288 (20) ◽  
pp. 14170-14177 ◽  
Author(s):  
Alexander V. Peskin ◽  
Nina Dickerhof ◽  
Rebecca A. Poynton ◽  
Louise N. Paton ◽  
Paul E. Pace ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Rate Constant ◽  
Active Site ◽  
Rate Constants ◽  
Active Sites ◽  
Order Rate Constant ◽  
The Other ◽  
Sulfenic Acid ◽  
Disulfide Formation ◽  
Fixed Concentration

Typical 2-Cys peroxiredoxins (Prxs) react rapidly with H2O2 to form a sulfenic acid, which then condenses with the resolving cysteine of the adjacent Prx in the homodimer or reacts with another H2O2 to become hyperoxidized. Hyperoxidation inactivates the Prx and is implicated in cell signaling. Prxs vary in susceptibility to hyperoxidation. We determined rate constants for disulfide formation and hyperoxidation for human recombinant Prx2 and Prx3 by analyzing the relative proportions of hyperoxidized and dimeric products using mass spectrometry as a function of H2O2 concentration (in the absence of reductive cycling) and in competition with catalase at a fixed concentration of H2O2. This gave a second order rate constant for hyperoxidation of 12,000 m−1 s−1 and a rate constant for disulfide formation of 2 s−1 for Prx2. A similar hyperoxidation rate constant for Prx3 was measured, but its rate of disulfide formation was ∼10-fold higher, making it is more resistant than Prx2 to hyperoxidation. There are two active sites within the homodimer, and at low H2O2 concentrations one site was hyperoxidized and the other present as a disulfide. Prx with two hyperoxidized sites formed progressively at higher H2O2 concentrations. Although the sulfenic acid forms of Prx2 and Prx3 are ∼1000-fold less reactive with H2O2 than their active site thiols, they react several orders of magnitude faster than most reduced thiol proteins. This observation has important implications for understanding the mechanism of peroxide sensing in cells.

The kinetics of internal energy randomisation in thermal unimolecular reactions

1980 ◽  
Vol 58 (21) ◽  
pp. 2236-2245 ◽  
Author(s):  
Huw Owen Pritchard
Keyword(s):  
Internal Energy ◽  
Lower Limit ◽  
Rate Constant ◽  
Rate Constants ◽  
Rate Function ◽  
Second Order ◽  
Specific Rate ◽  
Unimolecular Reactions ◽  
Methyl Isocyanide ◽  
Kinetics Of

The aim of this paper is to present a minimal theory of thermal unimolecular reactions, including explicitly the kinetics of intramolecular randomisation processes. A quasi-diatomic model is formulated and, within the framework of the model, both first-and second-order randomisation processes among reactant and product states are examined.It is concluded that a vital mechanism for the intramolecular energy randomisation in thermal unimolecular reactions is a collisional one. On this assumption, a straightforward derivation of the Polanyi–Wigner specific rate function, as we have reinterpreted it, becomes possible.At the same time, anomalies in the fall-off curves for the thermal isomerisations of methyl isocyanide and ethyl isocyanide can be accounted for very simply: in the former case, values for both the first- and second-order randomisation rate constants can be derived, but in the latter case it is only possible to establish a lower limit for the second-order randomisation rate constant.

scholarly journals HPLC INVESTIGATION OF THE DEGRADATION OF SOME ARTIFICIAL AZO FOOD COLORANTS IN THE PRESENCE OF ASCORBIC ACID

2017 ◽  
Vol 29 (1-2) ◽  
Author(s):  
Vesna Kostić ◽  
Trajče Stafilov ◽  
Kiro Stojanoski
Keyword(s):  
Ascorbic Acid ◽  
Rate Constant ◽  
Rate Constants ◽  
Half Life ◽  
The Other ◽  
Brilliant Blue ◽  
Food Colorants ◽  
Brilliant Blue Fcf ◽  
Patent Blue ◽  
Patent Blue V

A b s t r a c t: The influence of the concentration of ascorbic acid on some azo food colorant (Brilliant Black BN, Brilliant Blue FCF, Chinoline Yellow, Indigotine, Patent Blue V and Tartazine) degradation in the solution has been studied. Rate constant (k), time of colorant half-life (t1/2), as well as the type of the kinetic reaction have been determined. The colorants and the ascorbic acid have been determined by high performance liquid chromatography (HPLC) with diode array detector (DAD) and UV-VIS spectrometry. It was found that the higher concentration of ascorbic acid leads to the higher rate constant and lower colorants half-life. The values of the rate constants are 2.50–4.25 times higher when the colorant degradation was run in the presence of 500 mg L–1 of ascorbic acid than in the case of the presence of 100 mg L–1 ascorbic acid for Brilliant Blue FCF, Chinoline Yellow, Patent Blue V and Tartazine. From the other side, the degradation of Brilliant Black BN and Indigotine is very fast with a total degradation for 6–9 days. Therefore, the rate constants for those two food colorants are much higher than for the other investigated colorants. According to the linearity of the kinetics curves (ln(c/co) v.s. time) it appeared to be first order kinetics for the interval up to 4 days.

Functional Properties of p-Anisoylated Plasmin-Staphylokinase Complex

1993 ◽  
Vol 70 (02) ◽  
pp. 326-331 ◽  
Author(s):  
H R Lijnen ◽  
B Van Hoef ◽  
R A G Smith ◽  
D Collen
Keyword(s):  
Human Plasma ◽  
Rate Constant ◽  
Time Course ◽  
Bolus Injection ◽  
Similar Rate ◽  
Clot Lysis ◽  
Lag Phase ◽  
Plasma Clot ◽  
Rapid Clearance ◽  
Stoichiometric Complex

SummaryThe kinetic and fibrinolytic properties of a reversibly acylated stoichiometric complex between human plasmin and recombinant staphylokinase (plasmin-STAR complex) were evaluated. The acylation rate constant of plasmin-STAR by p-amidinophenyl-p’-anisate-HCI was 52 M-1 s-1 and its deacylation rate constant 1.2 × 10-4 s-1 (t½ of 95 min) which are respectively 50-fold and around 3-fold lower than for the plasmin-streptokinase complex. The acylated complex was stable as evidenced by binding to lysine-Sepharose. However, following an initial short lag phase, the acylated plasmin-STAR complex activated plasminogen at a similar rate as the unblocked complex, whereas the acylated plasmin-streptokinase complex did not activate plasminogen. These findings indicate that STAR, unlike streptokinase, dissociates from its acylated complex with plasmin in the presence of excess plasminogen. In agreement with this hypothesis, the time course of the lysis of a 125I-fibrin labeled plasma clot submerged in citrated human plasma, is similar for acylated plasmin-STAR, unblocked plasmin-STAR and free STAR (50% clot lysis in 2 h requires 12 nM of each agent). The plasma clearances of STAR-related antigen following bolus injection in hamsters were 1.0 to 1.5 ml/min for acylated plasmin-STAR, unblocked plasmin-STAR and free STAR, as a result of short initial half-lives of 2.0 to 2.5 min.The dissociation of the anisoylated plasmin-STAR complex and its consequent rapid clearance suggest that it has no apparent advantages as compared to free STAR for clinical thrombolysis.

A FACILE SYNTHESIS AND REACTIONS OF AMINO SELENOLO[2,3-b]PYRIDINE CARBOXYLATE

2015 ◽  
Vol 12 (1) ◽  
pp. 3910-3918 ◽  
Author(s):  
Dr Remon M Zaki ◽  
Prof Adel M. Kamal El-Dean ◽  
Dr Nermin A Marzouk ◽  
Prof Jehan A Micky ◽  
Mrs Rasha H Ahmed
Keyword(s):  
Biological Activity ◽  
Carbonyl Compounds ◽  
Mass Spectra ◽  
The Other ◽  
Pyridine Derivatives ◽  
Facile Synthesis ◽  
High Biological Activity ◽  
Basic Hydrolysis ◽  
Pyridine Carboxylate ◽  
Hydrolysis Of

 Incorporating selenium metal bonded to the pyridine nucleus was achieved by the reaction of selenium metal with 2-chloropyridine carbonitrile 1 in the presence of sodium borohydride as reducing agent. The resulting non isolated selanyl sodium salt was subjected to react with various α-halogenated carbonyl compounds to afford the selenyl pyridine derivatives 3a-f  which compounds 3a-d underwent Thorpe-Ziegler cyclization to give 1-amino-2-substitutedselenolo[2,3-b]pyridine compounds 4a-d, while the other compounds 3e,f failed to be cyclized. Basic hydrolysis of amino selenolo[2,3-b]pyridine carboxylate 4a followed by decarboxylation furnished the corresponding amino selenolopyridine compound 6 which was used as a versatile precursor for synthesis of other heterocyclic compound 7-16. All the newly synthesized compounds were established by elemental and spectral analysis (IR, 1H NMR) in addition to mass spectra for some of them hoping these compounds afforded high biological activity.

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

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