Reactions of α-isobutyl-α-(methylthio)methylene Meldrum's acid with primary amines in aqueous DMSO

2006 ◽  
Vol 84 (12) ◽  
pp. 1679-1685 ◽  
Author(s):  
Supriya Biswas ◽  
Mahammad Ali ◽  
Zvi Rappoport ◽  
Hatim Salim

The aminolysis of α-isobutyl-α-(methylthio)methylene Meldrum's acid 7 with primary amines, namely, n-butylamine, glycinamide, and methoxyethylamine in DMSO–H2O (50:50, v/v) at 20 °C is overall second-order but first-order in both 7 and amines. The reaction with aminoacetonitrile (AA) is overall third-order, first-order in substrate, and second-order in amine at low amine concentration, while at high amine concentration and high pH the dependence on amine is first-order. A general three-step mechanism has been proposed for all these reactions. For the former group of amines, the first step is a rate-limiting attack of the amine to form the tetrahedral intermediate (TA±), followed by a fast acid–base equilibrium and a fast RNH3+- or H2O-assisted leaving group expulsion. For AA, general base catalysis was confirmed from the dependence of kA on [AA]f and on [OH–]. For all four amines, a good Brønsted plot of log k1 vs. pKaAH in DMSO–H2O (50:50, v/v) with βnuc = 0.34 ± 0.02 was observed. These observations are consistent with the suggested mechanism.Key words: nucleophilic vinylic substitution reactions, primary amines, α-isobutyl-α-(methylthio)methylene Meldrum's acid, three-step mechanism.

2009 ◽  
Vol 74 (1) ◽  
pp. 43-55 ◽  
Author(s):  
Dennis N. Kevill ◽  
Byoung-Chun Park ◽  
Jin Burm Kyong

The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.


1999 ◽  
Vol 77 (5-6) ◽  
pp. 584-594 ◽  
Author(s):  
Claude F Bernasconi ◽  
Rodney J Ketner ◽  
Xin Chen ◽  
Zvi Rappoport

The reaction of thiomethoxybenzylidene Meldrum's acid (5-SMe) with thiolate and alkoxide ion nucleophiles is shown to proceed by the two-step addition-elimination SNV mechanism in which the tetrahedral intermediate accumulates to detectable levels. For the reactions with thiolate ions, rate constants for nucleophilic addition (k1RX), its reverse (k-1RX), and for conversion of the intermediate to products (k2RX) were determined. For the reactions with alkoxide ions, only k1RX and k-1RX could be obtained; the intermediate in these reactions did not yield the expected substitution products, and hence no k2RX values could be determined. The reactions with OH- and water are believed to follow the same mechanism, but the respective intermediates remain at steady-state levels, and only k1OH and k1H²O for nucleophilic attack on 5-SMe were measurable. New insights regarding structure-reactivity behavior in SNV reactions are gained from comparisons of rate and equilibrium constants in the reactions of 5-SMe with the corresponding parameters in the reactions of methoxybenzylidene Meldrum's acid (5-OMe) and benzylidene Meldrum's acid (5-H). In particular, the relative importance of steric and pi-donor effects of the MeS vs. MeO group in 5-SMe and 5-OMe, respectively, and their role in affecting the intrinsic rate constants for nucleophilic addition, has been clarified by these comparisons. Our results also add support to a previous suggestion that soft-soft type interactions tend to increase intrinsic rate constants for thiolate ion addition to vinylic substrates, especially 5-SMe with the soft MeS group.Key words: nucleophilic vinylic substitution, intrinsic rate constants, transition state imbalances, steric/pi-donor/anomeric effects.


2002 ◽  
Vol 57 (11) ◽  
pp. 1320-1326 ◽  
Author(s):  
H. A. A. Medien

The condensation reaction of Meldrum’s acid with aromatic aldehydes in the presence of a catalyst has been investigated spectrophotometrically at 25-50 °C. The reaction follows overall second order kinetics, first order in each of the reactants. Electron-withdrawing groups accelerate and electron-releasing groups retard the rate of condensation. From the dependence of the rate constants on temperature, the activation parameters have been calculated and also the isokinetic temperature with a value of 403.5 K. Based on this reaction, determination of eight aromatic aldehydes in a concentration range of 1.49 - 91 μg/ml is proposed. On the other hand, determination of some aromatic aldehydes with Meldrum’s acid is performed in water at 75 °C for 2 h, without adding any catalyst.


1997 ◽  
Vol 36 (04/05) ◽  
pp. 315-318 ◽  
Author(s):  
K. Momose ◽  
K. Komiya ◽  
A. Uchiyama

Abstract:The relationship between chromatically modulated stimuli and visual evoked potentials (VEPs) was considered. VEPs of normal subjects elicited by chromatically modulated stimuli were measured under several color adaptations, and their binary kernels were estimated. Up to the second-order, binary kernels obtained from VEPs were so characteristic that the VEP-chromatic modulation system showed second-order nonlinearity. First-order binary kernels depended on the color of the stimulus and adaptation, whereas second-order kernels showed almost no difference. This result indicates that the waveforms of first-order binary kernels reflect perceived color (hue). This supports the suggestion that kernels of VEPs include color responses, and could be used as a probe with which to examine the color visual system.


2017 ◽  
Vol 9 (3) ◽  
pp. 17-30
Author(s):  
Kelly James Clark

In Branden Thornhill-Miller and Peter Millican’s challenging and provocative essay, we hear a considerably longer, more scholarly and less melodic rendition of John Lennon’s catchy tune—without religion, or at least without first-order supernaturalisms (the kinds of religion we find in the world), there’d be significantly less intra-group violence. First-order supernaturalist beliefs, as defined by Thornhill-Miller and Peter Millican (hereafter M&M), are “beliefs that claim unique authority for some particular religious tradition in preference to all others” (3). According to M&M, first-order supernaturalist beliefs are exclusivist, dogmatic, empirically unsupported, and irrational. Moreover, again according to M&M, we have perfectly natural explanations of the causes that underlie such beliefs (they seem to conceive of such natural explanations as debunking explanations). They then make a case for second-order supernaturalism, “which maintains that the universe in general, and the religious sensitivities of humanity in particular, have been formed by supernatural powers working through natural processes” (3). Second-order supernaturalism is a kind of theism, more closely akin to deism than, say, Christianity or Buddhism. It is, as such, universal (according to contemporary psychology of religion), empirically supported (according to philosophy in the form of the Fine-Tuning Argument), and beneficial (and so justified pragmatically). With respect to its pragmatic value, second-order supernaturalism, according to M&M, gets the good(s) of religion (cooperation, trust, etc) without its bad(s) (conflict and violence). Second-order supernaturalism is thus rational (and possibly true) and inconducive to violence. In this paper, I will examine just one small but important part of M&M’s argument: the claim that (first-order) religion is a primary motivator of violence and that its elimination would eliminate or curtail a great deal of violence in the world. Imagine, they say, no religion, too.Janusz Salamon offers a friendly extension or clarification of M&M’s second-order theism, one that I think, with emendations, has promise. He argues that the core of first-order religions, the belief that Ultimate Reality is the Ultimate Good (agatheism), is rational (agreeing that their particular claims are not) and, if widely conceded and endorsed by adherents of first-order religions, would reduce conflict in the world.While I favor the virtue of intellectual humility endorsed in both papers, I will argue contra M&M that (a) belief in first-order religion is not a primary motivator of conflict and violence (and so eliminating first-order religion won’t reduce violence). Second, partly contra Salamon, who I think is half right (but not half wrong), I will argue that (b) the religious resources for compassion can and should come from within both the particular (often exclusivist) and the universal (agatheistic) aspects of religious beliefs. Finally, I will argue that (c) both are guilty, as I am, of the philosopher’s obsession with belief. 


2020 ◽  
Vol 23 (23) ◽  
pp. 2626-2634
Author(s):  
Saiedeh Kamalifar ◽  
Hamzeh Kiyani

: An efficient and facial one-pot synthesis of 4-aryl-3,4-dihydrobenzo[g]quinoline- 2,5,10(1H)-triones was developed for the first time. The process proceeded via the three-component cyclocondensation of 2-amino-1,4-naphthoquinone with Meldrum’s acid and substituted benzaldehydes under green conditions. The fused 3,4-dihydropyridin-2(1H)- one-ring naphthoquinones have been synthesized with good to high yields in refluxing ethanol as a green reaction medium. This protocol is simple and effective as well as does not involve the assistance of the catalyst, additive, or hazardous solvents.


Author(s):  
Uriah Kriegel

Brentano’s theory of judgment serves as a springboard for his conception of reality, indeed for his ontology. It does so, indirectly, by inspiring a very specific metaontology. To a first approximation, ontology is concerned with what exists, metaontology with what it means to say that something exists. So understood, metaontology has been dominated by three views: (i) existence as a substantive first-order property that some things have and some do not, (ii) existence as a formal first-order property that everything has, and (iii) existence as a second-order property of existents’ distinctive properties. Brentano offers a fourth and completely different approach to existence talk, however, one which falls naturally out of his theory of judgment. The purpose of this chapter is to present and motivate Brentano’s approach.


Author(s):  
Tim Button ◽  
Sean Walsh

In this chapter, the focus shifts from numbers to sets. Again, no first-order set theory can hope to get anywhere near categoricity, but Zermelo famously proved the quasi-categoricity of second-order set theory. As in the previous chapter, we must ask who is entitled to invoke full second-order logic. That question is as subtle as before, and raises the same problem for moderate modelists. However, the quasi-categorical nature of Zermelo's Theorem gives rise to some specific questions concerning the aims of axiomatic set theories. Given the status of Zermelo's Theorem in the philosophy of set theory, we include a stand-alone proof of this theorem. We also prove a similar quasi-categoricity for Scott-Potter set theory, a theory which axiomatises the idea of an arbitrary stage of the iterative hierarchy.


Author(s):  
Huineng Wang ◽  
Yanfeng Guo ◽  
Yungang Fu ◽  
Dan Li

This study introduces the opinion of the corrugation hierarchy to develop the second-order corrugation paperboard, and explore the deformation characteristics, yield strength, and energy absorbing capacity under out-of-plane static evenly compression loading by experimental and analytical approaches. On the basis of the inclined-straight strut elements of corrugation unit and plastic hinge lines, the yield and crushing strengths of corrugation unit were analyzed. This study shows that as the compressive stress increases, the second-order corrugation core layer is firstly crushed, and the first-order corrugation structures gradually compacted until the failure of entire structure. The corrugation type has an obvious influence on the yield strength of the corrugation sandwich panel, and the yield strength of B-flute corrugation sandwich panel is wholly higher than that of the C-flute structure. At the same compression rate, the flute type has a significant impact on energy absorption, and the C-flute second-order corrugation sandwich panel has better bearing capacity than the B-flute structure. The second-order corrugation sandwich panel has a better bearing capacity than the first-order structure. The static compression rate has little effect on the yield strength and deformation mode. However, with the increase of the static compression rate, the corrugation sandwich panel has a better cushioning energy absorption and material utilization rate.


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