Kinetics and mechanism of oxidation of aspirin by bromamine-T,N-bromosuccinimide,and N-bromophthalimide

The kinetics of the oxidation of aspirin (ASP) by bromamine-T (BAT), N-bromosuccinimide (NBS), and N-bromophthalimide (NBP) has been studied in aqueous perchloric acid at 303 K. The oxidation reaction follows identical kinetics with first-order in [oxidant], fractional-order in [ASP], and inverse fractional-order in [H⁺]. Under identical experimental conditions the extent of oxidation with different oxidizing agents is in the order: NBS>BAT>NBP. The rate decreased with decreasing dielectric constant of the medium. The variation of ionic strength and the addition of the reaction products and halide ions had no significant effect on the reaction rate. The solvent isotope effect was studied using D₂O. Kinetic parameters were evaluated by studying the reaction at different temperatures. The reaction products were identified by GC–MS. The proposed reaction mechanism and the derived rate law are consistent with the observed kinetic data. Formation and decomposition constants for ASP-oxidant complexes have been evaluated. Decarboxylation, bromination, and loss of acetic acid gave 2,4,6-tribromophenol. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 407–414, 1998     

Syntheses, characterization, and X-ray crystal structures of beta-diketiminate group 13 hydrides, chlorides, and fluorides

A series of organometallic compounds of group 13 metals supported by the sterically encumbered beta-diketiminate ligand containing hydrides, fluorides, chlorides, and bromide have been synthesized and structurally characterized. The synthetic strategy applied utilizes halide metathesis and reduction of metal chlorides to the corresponding hydrides. Thus, the reaction of LLi.OEt2 with MeMCl2 affords LM(Me)Cl (M = Al (1), Ga (2), In (3)) and LGaBr2 (4) with GaBr3. Reduction of LGa(Me)Cl with LiH.BEt3 leads to the formation of LGa(Me)H (10). Synthesis of LGaH(2) (12) has been accomplished by reacting LGaI2 (8) with LiH.BEt3. LAl(Me)Cl (1) and LAlH2 (6) have been converted to LAl(Me)F (5) and LAlF2 (7), respectively. The former was obtained in a reaction of LAl(Me)Cl with Me3SnF while the latter was isolated in a reaction of LAlH2 with BF3.OEt2. Similarly reaction of LGaI2 (8) with Me3SnF affords LGaF2 (9). Compounds reported herein have been characterized by elemental analyses, IR, NMR, EI-MS, and single-crystal X-ray diffraction techniques.     

Basic and applied features of multicopper oxidases, CueO, bilirubin oxidase, and laccase

Multicopper oxidases (MCOs) such as CueO, bilirubin oxidase, and laccase contain four Cu centers, type 1 Cu, type II Cu, and a pair of type III Cu's in a protein molecule consisting of three domains with homologous structure to cupredoxin containing only type I Cu. Type I Cu mediates electron transfer between the substrate and the trinuclear Cu center formed by a type II Cu and a pair of type III Cu's, where the final electron acceptor O(2) is converted to H(2)O without releasing activated oxygen species. During the process, O(2) is reduced by MCOs such as lacquer laccase and bilirubin oxidase; the reaction intermediate II with a possible doubly OH(-)-bridged structure in the trinuclear Cu center has been detected. The preceding reaction intermediate I has been detected by the reaction of the lacquer laccase in a mixed valence state, at which type I Cu was cuprous and the trinuclear Cu center was fully reduced, and by the reaction of the Cys --> Ser mutant for the type I Cu site in bilirubin oxidase and CueO. An acidic amino acid residue located adjacent to the trinuclear Cu center was proved to function as a proton donor to these reaction intermediates. The substrate specificity of MCO for organic substrates is produced by the integrated effects of the shape of the substrate-binding site and the specific interaction of the substrate with the amino acid located adjacent to the His residue coordinating to the type I Cu. In contrast, the substrate specificity of the cuprous oxidase, CueO, is produced by the segment covering the Cu(I)-binding site so as to obstruct the access of organic substrates. Truncating the segment spanning helix 5 to helix 7 greatly reduced the specificity of CueO for Cu(I) and prominently enhanced the low oxidizing activity for the organic substrates, indicating the success of protein engineering to modify the substrate specificity of MCO.     

Synthesis,characterization, and thermal properties of anhydride terminated and allyl terminated oligoimides

This study concerns the synthesis of anhydride terminated oligoimides (ANTOI) and allyl terminated oligoimides (ALTOI), in acetic acid medium, which allows a very fast reaction and an easy working out. For the preparation of ALTOIs, two methods are compared: the first one consists of adding the monofunctional compound (allyl amine) to the ANTOI already formed during a first step by reaction of a dianhydride (excess) and a diamine. The second method consists of a “one pot” reaction between the dianhydride, the diamine, and the monofunctional allyl–amine compounds, at the beginning of the reaction. The experimental results show that the best control of the molecular weights is obtained with the first method. If the amount of allyl amine is higher than the amount necessary to end cap the ANTOI, a transimidization reaction occurs. Thermal analyses of oligoimides terminated by anhydride or allyl groups have been performed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Transition and thermoresistance properties make ANTOI and ALTOI derivatives interesting as precursors for block polyimide copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2993–3003, 2000     

Carbamates,thiolcarbamates, dithiocarbamates and thioncarbamates derived from 2-benzothiazolinone and benzoxazolinone

The reaction of 3-(2-hydroxyethyl)-2-benzothiazoline with methyl, phenyl isocyanate, or dimethylcarbamoyl chloride afforded the carbamates 1–4 . The carbanilate 5 was prepared by the reaction of 2-benzothiazolinone with 3-chloropropyl-N-methylcarbanilate under basic conditions. The reaction of the appropriate 2-benzothiazolinone with the appropriate 2-chloro or 3-chloropropyl disubstituted thiolcarbamate under basic conditions furnished the thiolcarbamates 6–14 . The thiolcarbamate 15 was prepared by the reaction of sodium di-isopropylthiolcarbamate with 3-(chloromethyl)-2-benzothiazolinone. The reaction of 3-(chloromethyl)-2-ben-zothiazolinone and related compound with the appropriate sodium or triethylamine salt of disubstituted dithiocarbamate afforded the dithiocarbamate 16–22 . The reaction of the appropriate xanthate with the potassium salt of bromoacetic acid and the appropriate secondary amine afforded the thionocarbamates 23–29 . The thionocarbamate 30 was synthesized by the reaction of 5-chloro-2-benzothiazolinone with 3-chloropropyl diethylthionocarbamate.     

Biomimetic total synthesis of litseaverticillols B, E, I, and J and structural reassignment of litseaverticillol E

[reaction: see text] The first total synthesis of litseaverticillols B (1), E (2), I (4), and J (5) as well as the structural reassignment of litseaverticillol E (2) have been achieved by means of a biomimetic sequence of transformations during which a [4 + 2]-initiated reaction cascade and an ene reaction, both involving singlet oxygen ((1)O(2)), formed key steps. The reassignment of the structure of litseaverticillol E (3) to include an allylic hydroperoxide provides strong support for our biogenetic hypothesis.     

Polymerization of diethynyldiphenylmethane: DSC,FTIR, NMR,and dielectric characterization

4,4′-Diethynyldiphenylmethane thermally polymerizes by a free radical mechanism to a highly crosslinked structure of interest as a high temperature composite matrix resin. The polymerization reaction was characterized by differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, and microdi-electrometry. The predominant reaction mechanism appears to be linear polymerization through the acetylene end groups, which follows first-order kinetics. However, during the early stages of reaction a second, more rapid polymerization mechanism is evident; it is postulated that this is the formation of a cyclic trimer, which is kinetically favored but sterically prohibited as the crosslinked network grows. Formation of a liquid crystalline trimer is hyppthesized; such intermediate formation is supported by intensity increases in the aromatic region of the NMR spectra, by FTIR difference spectroscopy comparisons with model compounds, and by enhancement of conductivity as observed by microdielectrometry.     

Tertiary Acetylenic Alcohols,Ethers, and Esters on the Basis of Isocamphanone,Camphor, Fenchone,Isofenchone, and Adamanthanone

Acetylenic lithium alcoholates were synthesized by reactions of 1-hexyne, 1-octyne, and phenylacetylene with butyllithium with subsequent reaction of the resulting acetylides with isocamphanone, (±)-camphor, (+)-fenchone, isofenchone, and adamanthanone. The latter reaction is controlled by steric factors. Lithium alcoholates were used to synthesize the corresponding alcohols, ethers, and esters. Configurational assessment of the products was performed on the basis of quantum-chemical calculations and X-ray diffraction analysis.     

Synthesis of Difluoroglycine Derivatives from Amines,Difluorocarbene, and CO2: Computational Design,Scope, and Applications

A three-component reaction (3CR) for the synthesis of difluoroglycine derivatives has been achieved by using amines, difluorocarbene (generated in situ), and the abundant, inexpensive, and nontoxic C₁ source CO₂. Various tert-amines and pyridine, (iso)quinoline, imidazole, thiazole, and pyrazole derivatives were incorporated, and the corresponding products were isolated in solid form without purification by column chromatography on silica gel. Detailed reaction profiles of the 3CR were obtained from computational analysis using DFT calculations, and the results critically suggest that simple ammonia is not applicable to this reaction. In addition, as strongly supported by computational predictions, a new reagent that can generate difluorocarbene at 0 °C without any additives was discovered. Finally, radical substitution reactions of the obtained difluoroglycine derivatives under photoredox conditions, as well as a synthetic application as an N-heterocyclic carbene ligand are shown.     

Nitrosation, thiols, and hemoglobin: energetics and kinetics

Nitrosothiols are powerful vasodilators. Although the mechanism of their formation near neutral pH is an area of intense research, neither the energetics nor the kinetics of this reaction or of subsequent reactions have been addressed. The following considerations may help to guide experiments. (1) The standard Gibbs energy for the homolysis reaction RSNO → RS(?) + NO(?)(aq) is +110 ± 5 kJ mol(-1). (2) The electrode potential of the RSNO, H(+)/RSH, NO(?)(aq) couple is -0.20 ± 0.06 V at pH 7. (3) Thiol nitrosation by NO(2)(-) is favorable by 37 ± 5 kJ mol(-1) at pH 7. (4) N(2)O(3) is not involved in in vivo nitrosation mechanisms for thermodynamic--its formation from NO(2)(-) costs 59 kJ mol(-1)--or kinetic--the reaction being second-order in NO(2)(-)--reasons. (5) Hemoglobin (Hb) cannot catalyze formation of N(2)O(3), be it via the intermediacy of the reaction of Hb[FeNO(2)](2+) with NO(?) (+81 kJ mol(-1)) or reaction of Hb[FeNO](3+) with NO(2)(-) (+88 kJ mol(-1)). (6) Energetically and kinetically viable are nitrosations that involve HNO(2) or NO(?) in the presence of an electron acceptor with an electrode potential higher than -0.20 V. These considerations are derived from existing thermochemical and kinetics data.     

Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining

A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Po?lya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).     

The reaction of o-alkynylarene and heteroarene carboxaldehyde derivatives with iodonium ions and nucleophiles: a versatile and regioselective synthesis of 1H-isochromene, naphthalene, indole, benzofuran, and benzothiophene compounds

The reaction of o-alkynylbenzaldehydes 1 with different alcohols, silylated nucleophiles 5, electron-rich arenes 10, and heteroarenes 12 in the presence of the reagent IPy(2)BF(4), at room temperature, gave functionalized 4-iodo-1H-isochromenes 2, 6, 11, and 13 in a regioselective manner. When alkynes 16 and alkenes 19 and 20 were used as nucleophiles, a regioselective benzannulation reaction took place to form 1-iodonaphthalenes 17 and 1-naphthyl ketones 18, respectively. Moreover, the latter process has been adapted to accomplish the synthesis of indole, benzofuran, and benzothiophene derivatives (23, 27, and 28, respectively). The three patterns of reactivity observed for the o-alkynylbenzaldehyde derivatives with IPy(2)BF(4) stem from a common iodinated isobenzopyrylium ion intermediate, A, that evolves in a different way depending on the nucleophile present in the reaction medium. A mechanism is proposed and the different reaction pathways observed as a function of the type of nucleophile are discussed. Furthermore, the reaction of the o-hexynylbenzaldehyde 1 b with styrene was monitored by NMR spectroscopy. Compound III, a resting state for the common intermediate in the absence of acid, has been isolated. Its evolution in acid media has been also tested, thereby providing support to the proposed mechanism.     

Photoinduced tandem three-component coupling of propanedinitrile, 2,5-dimethylhexa-2,4-diene, and cyanoarenes

A tandem three-component coupling photoreaction proceeds upon photoirradiation of MeCN/H2O solutions containing propanedinitrile (1, malononitrile), 2,5-dimethylhexa-2,4-diene (2), and polycyanoarenes in the presence of phenanthrene and carbonate, leading to selective alpha-monoalkylation of 1. The reaction proceeds via photo-NOCAS (Nucleophile-Olefin Combination, Aromatic Substitution) type mechanism: nucleophilic attack of the anion of 1 to photogenerated 2(*+) is followed by ipso-substitution on the radical anion of the polycyanoarene. It advances under mild, safe, and environmentally friendly conditions such as proceeding at ambient temperature without metals and halogens, and in the presence of weak base. The reaction also represents a novel and metal-free cross-coupling reaction that leads to ipso-substitution on polycyanoarene via aryl-cyano bond cleavage. In addition, the reaction is a rare example of introducing carbon nucleophile in the photoinduced electron transfer reaction, except that of cyanide ion.     

Controlled synthesis of high-quality PbS star-shaped dendrites, multipods, truncated nanocubes, and nanocubes and their shape evolution process

Well-defined single-crystalline PbS nano- and microstructures including dendrites, multipods, truncated nanocubes, and nanocubes were synthesized in high yield by a simple solution route. Novel star-shaped PbS dendrites with six symmetric arms along the 100 direction, each of which shows one trunk (long axis) and four branches (short axes), have been achieved using Pb(AC)2 and thioacetamide (TAA) as precursors, under the molar ratio Pb(AC)2/TAA = 2/1, at initial reaction temperature 80 degrees C, refluxing for 30 min at 100 degrees C, in the presence of cetyltrimethylammonium bromine (CTAB). The "nanorods" in each branch are parallel to each other in the same plane and are perpendicular to the trunk. The truncated nanocubes mainly bounded by the {100} plane were prepared under a different Pb(AC)2/TAA molar ratio, at initial reaction temperature 40 degrees C, refluxing for 12 h at 100 degrees C. Based on the systematic studies on their shape evolution, a possible growth mechanism of these PbS nano- and microstructures was proposed. The shapes of PbS nanocrystals with face-centered cubic (fcc) structure are mainly determined by the ratio (R) between the growth rates along the (100) and (111) directions. The Pb(AC)2/TAA molar ratio and the initial reaction temperature influence the growth ratio R in the formation of PbS nuclei at an early stage, which results in the final morphology of PbS nanocrystals. Under the current experimental conditions, we can control the PbS shape evolution by simply tuning the molar ratio, the initial reaction temperature, and the period of reaction. Based on the systematic studies on the shape evolution, this approach is expected to be employed for the control-shaped synthesis of other fcc structural semiconductor nanomaterials. The photoluminescence properties were investigated and the prepared nano- and microstructures displayed a very strong luminescence around 600-650 nm at room temperature.     

The formation of charge-transfer complexes from N-vinylindole and chlorine,bromine, and iodine

The reaction of vinylindole with bromine, chlorine, and iodine in CCl₄ solution in the cold leads to the formation of charge-transfer complexes (CTC). The formation of CTC has been confirmed by a study of the physicochemical properties and the IR and UV spectra of the reaction products.     

Synthesis,structures, and properties of new sterically hindered hydrazine-based catecholaldimines

New sterically hindered catecholaldimines derived from hydrazine were synthesized in high yields. Two procedures for the synthesis of sterically hindered catecholaldimines were developed: by the reaction of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde with hydrazines (hydrazine hydrate, phenyl-, 1,1-diphenyl-, and (diphenylmethylene)hydrazines, acetyl and benzoyl hydrazides) or by the reaction of 3,5-di-tert-butyl-6-(hydrazonomethyl)catechol with a carbonyl compound (the reaction with 4-N,N-dimethylaminobenzaldehyde). The X-ray diffraction analysis and IR, UV, and NMR spectroscopic studies showed that these compounds exist in the catecholic form both in solution and the crystalline state.     

Layered double hydroxide supported nanopalladium catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes

Layered double hydroxide and Merrifield resin supported nanopalladium(0) catalysts are prepared by an exchange of PdCl(4)(2-) followed by reduction and well characterized for the first time. The ligand-free heterogeneous layered double hydroxide supported nanopalladium (LDH-Pd(0)) catalyst using the basic LDH in place of basic ligands indeed exhibits higher activity and selectivity in the Heck olefination of electron-poor and electron-rich chloroarenes in nonaqueous ionic liquids (NAIL) over the homogeneous PdCl(2) system. Using microwave irradiation, the rate of the Heck olefination reaction is accelerated, manifold with the highest turnover frequency ever recorded in the case of both electron-poor and electron-rich chloroarenes. The basic LDH-Pd(0) shows a superior activity over a range of supported catalysts, from acidic to weakly basic Pd/C, Pd/SiO(2,) Pd/Al(2)O(3), and resin-PdCl(4)(2-) in the Heck olefination of deactivated electron-rich 4-chloroanisole. The use of LDH-Pd(0) is extended to the Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes in an effort to understand the scope and utility of the reaction. The catalyst is quantitatively recovered from the reaction by a simple filtration and reused for a number of cycles with almost consistent activity in all the coupling reactions. The heterogeneity studies provide an insight into mechanistic aspects of the Heck olefination reaction and evidence that the reaction proceeds on the surface of the nanopalladium particles of the heterogeneous catalyst. TEM images of the fresh and used catalyst indeed show that the nanostructured palladium supported on LDH remains unchanged at the end of the reaction, while the XPS and evolved gas detection by TGA-MS of the used catalyst identify ArPdX species on the heterogeneous surface. Thus, the ligand-free nanopalladium supported on LDH, synthesized by the simple protocol, displays superior activity over the other heterogeneous catalysts inclusive of nanopalladium in the C-C coupling reactions of chloroarenes.     

Synthesis, properties, and redox behavior of mono-, bis-, and tris[1,1,4,4,-tetracyano-2-(1-azulenyl)-3-butadienyl] chromophores binding with benzene and thiophene cores

Mono-, bis-, tris-, and tetrakis(1-azulenylethynyl)benzene and mono- and bis(1-azulenylethynyl)thiophene derivatives 5-10 have been prepared by Pd-catalyzed alkynylation of ethynyl arenes with 1-iodoazulene derivative or the 1-ethynylazulene derivative with tetraiodobenzene and iodothiophenes under Sonogashira-Hagihara conditions. Compounds 5-10 reacted with tetracyanoethylene in a [2+2] cycloaddition reaction to afford the corresponding 1,1,4,4,-tetracyano-2-(5-isopropyl-3-methoxycarbonyl-1-azulenyl)-3-butadienyl chromophores 12-16 in excellent yields, except for the reaction of the tetrakis(1-azulenylethynyl)benzene derivative. 1,1,4,4,-Tetracyano-2,3-bis(1-azulenyl)butadiene (17) was also prepared by the similar reaction of bis(1-azulenyl)acetylene (11) with tetracyanoethylene (TCNE). The redox behavior of novel azulene derivatives 12-17 was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.     

Copper-catalyzed, one-pot, three-component synthesis of benzimidazoles by condensation and C-N bond formation

Benzimidazoles were synthesized by the copper-catalyzed, one-pot, three-component reaction of 2-haloanilines, aldehydes, and NaN(3). The reaction was optimized when 2-iodo- or 2-bromoanilines (1.0 equiv), aldehydes (1.2 equiv), NaN(3) (2.0 equiv), 5 mol% of CuCl, and 5 mol % of TMEDA were reacted in DMSO at 120 °C for 12 h. Good yields resulted, and the reaction showed tolerance toward functional groups such as ester, nitro, and chloro. Aliphatic and heteroaromatic aldehydes also afforded the desired products in moderate to good yields.     

Tetrabutylammonium salt induced denitration of nitropyridines: synthesis of fluoro-, hydroxy-, and methoxypyridines

An efficient method for the synthesis of fluoropyridines via the fluorodenitration reaction is reported. The reaction is mediated by tetrabutylammonium fluoride (TBAF) under mild conditions without undue regard to the presence of water. The fluorodenitration is general for 2- or 4-nitro-substituted pyridines, while 3-nitropyridines require attendant electron-withdrawing groups for the reaction to proceed efficiently. Nitropyridines also undergo hydroxy- and methoxydenitration under mild conditions in the presence of the corresponding tetrabutylammonium species. [reaction: see text]