Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3

TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed.     

Reactions of 1-hydroxy-1-methylethyl radicals with NO2-: time-resolved electron spin resonance

The reaction of the alpha-hydroxyalkyl radical of 2-propanol (1-hydroxy-1-methylethyl radical) with nitrite ions was characterized. A product of the reaction was assigned as the adduct nitro radical anion, [HO-C(CH(3))(2)NO(2)](*-). This radical was identified using time-resolved electron spin resonance (TRESR). The radical's magnetic parameters, the nitrogen hyperfine coupling constant (a(N) = 26.39 G), and its g-factor (2.0052) were the same as those of the nitro radical anion previously discovered in (*)OH spin-trapping experiments with the aci-anion of (CH(3))(2)CHNO(2). Production of [HO-C(CH(3))(2)NO(2)](*-) was determined to be 38% +/- 4% of the reaction of (CH(3))(2)C(*)-OH with nitrite. The reason why this fraction was less than 100% was rationalized by invoking the competitive addition at oxygen, which forms [HO-C(CH(3))(2)ONO](*-), followed by a rapid loss of (*)NO. Furthermore, by taking this mechanism into account, the bimolecular rate constant for the total reaction of (CH(3))(2)C(*)-OH with nitrite at reaction pH 7 was determined to be 1.6 x 10(6) M(-1) s(-1), using both decay traces of (CH(3))(2)C(*)-OH and growth traces of [HO-C(CH(3))(2)NO(2)](*-). This correspondence further confirms the nature of the reaction. The reaction mechanism is discussed with guidance by computations using density functional theory.     

Reactions of 3-(4-Aryl-2-thiazolyl)- and 3-(2-Benzothiazolyl)-2-iminocoumarins with N-Nucleophiles

The reaction of 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)-2-iminocoumarins with N-nucleophiles was studied. This reaction gives 2-N-substituted 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)iminocourmarins. N-Nucleophiles such as arylamines, heterocyclic amines, and hydrazine derivatives undergo this reaction.     

Kinetics Investigation of OH reaction with isoprene at 240-340 K and 1-3 torr using the relative rate/discharge flow/mass spectrometry technique

The kinetics of the reaction of OH radical with isoprene has been investigated at a total pressure of 1-3 Torr over a temperature range of 240-340 K using the relative rate/discharge flow/mass spectrometry (RR/DF/MS) technique. The reaction of isoprene with OH was found to be independent of pressure over the pressure range of 1-3 Torr at 298 K, and the reaction had reached its high-pressure limit at 1 Torr. However, the rate constant of this reaction is found to positively depend on pressure at 1-3 Torr and 340 K. At 298 K, the rate constant of this reaction was determined to be k1 = (10.4 +/- 1.9) x 10(-11) cm3 molecule(-1) s(-1), which is in good agreement with literature values. The Arrhenius expression for this reaction was determined to be k1 = (2.33 +/- 0.09) x 10(-11) exp[(444 +/- 27)/T] cm3 molecule(-1) s(-1) at 240-340 K. The atmospheric lifetime of isoprene was estimated to be 2.9 h based on the rate constant of isoprene + OH determined at 277 K in the present work.     

Generation of free radicals at subzero temperatures. III. Polyamine–hydroperoxide–iron system

The mechanism of the reaction of tetraethylenepentamine (TEPA) with cumene hydroperoxide (CHP) and iron ions was investigated. It was found that (1) TEPA did not reduce Fe(III); (2) TEPA was consumed by this reaction; (3) both Fe(II) and Fe(III) were effective for this reaction. It was shown that though the O? O bond of a hydroperoxide could be cleaved only at elevated temperatures, it could be easily cleaved by the reaction with the iron–TEPA complex. The function of this iron–TEPA complex is discussed.     

Transesterification of Ethylene Carbonate with Dimethyl Terephthalate over Various Metal Acetate Catalysts

IntroductionDimethyl carbonate(DMC) is known to be a novelbuilding block in organic synthesis. As an environmen-tally benign compound and a unique intermediate,DMC has attracted much attention[1,2]. Among the va-rious methods for synthesizing DMC, the tra…     

Reaction of Cobalt(III) Diaquatetrammine Cation with 5-(3-Nitrophenyl)tetrazole

A series of cobalt(III) tetrazolate tetrammine complexes were prepared by reaction of cobalt(III) diaquatetraammine perchlorate with 5-(3-nitrophenyl)tetrazole. The factors affecting this reaction were studied. The reaction was thermally activated both by common heating with an external heater and microwave heating. Thermolysis of the tetrazolate complexes was studied.     

Gold-nanoparticle-catalyzed synthesis of propargylamines: the traditional A3-multicomponent reaction performed as a two-step flow process

The alkyne, aldehyde, amine A(3)-coupling reaction, a traditional multicomponent reaction (MCR), has been investigated as a two-step flow process. The implicated aminoalkylation reaction of phenylacetylene with appropriate aldimine intermediates was catalyzed by gold nanoparticles impregnated on alumina. The aldimine formation was catalyzed by Montmorillonite K10 beforehand. The performance of the process has been investigated with respect to different reaction regimes. Usually, the A(3)-multicomponent reaction is performed as a "one-pot" process. Diversity-oriented syntheses using MCRs often have the shortcoming that only low selectivity and low yields are achieved. We have used a flow-chemistry approach to perform the A(3)-MCR in a sequential manner. In this way, the reaction performance was significantly enhanced in terms of shortened reaction time, and the desired propargylamines were obtained in high yields.     

A RuH(2)(CO)(PPh(3))(3)-catalyzed regioselective arylation of aromatic ketones with arylboronates via carbon-hydrogen bond cleavage

When the reaction of aromatic ketones with arylboronates (arylboronic acid esters) using RuH(2)(CO)(PPh(3))(3) (3) as a catalyst was conducted in toluene, the corresponding arylation product was obtained in moderate yields. In this case, a nearly equivalent amount of a benzyl alcohol derived from a reduction of an aromatic ketone was also formed. The use of aliphatic ketones, such as pinacolone and acetone, as an additive or a solvent dramatically suppressed the reduction of the aromatic ketones and, as a result, ortho-arylation products were obtained in high yield based on the aromatic ketones. In these reactions, the aliphatic ketone functioned as a scavenger of ortho-hydrogens of the aromatic ketones and the B(OR)(2) moiety of the arylboron compound (HB species). A variety of aromatic ketones, such as acetophenones, acetonaphthones, tetralones, and benzosuberone, could also be used in this coupling reaction. Several arylboronates containing electron-donating (NMe(2), OMe, and Me) and -withdrawing (CF(3) and F) groups were also applicable to this coupling reaction. Intermolecular competitive reaction using pivalophenone-d(0)() and -d(5) and intramolecular competitive reaction using pivalophenone-d(1) were carried out using 3 as a catalyst. The k(H)/k(D) value for the intermolecular competitive reaction was substantially different, compared with intramolecular competitive reaction. This strongly suggests the production of an intermediate where the ketone carbonyl is coordinated to the ruthenium involved in this catalytic reaction. (1)H and (11)B NMR studies using 2'-methylacetophenone, phenylboronate (2), and pinacolone (6) indicate that 6 functions effectively as a scavenger of the HB species.     

Direct conversion of carbonyl compounds into organic halides: indium(III) hydroxide-catalyzed deoxygenative halogenation using chlorodimethylsilane

The reaction of carbonyls and chlorodimethylsilane was effectively catalyzed by indium(III) hydroxide and afforded the corresponding deoxygenative chlorination products, in which the carbonyl carbon accepted two nucleophiles (H and Cl) with releasing oxygen. Only In(OH)3 catalyzed the reaction, and typical Lewis acids such as TiCl4, AlCl3, and BF3.OEt2 showed no catalytic activity. The reaction mechanism of this deoxygenative chlorination includes initial hydrosilylation followed by chlorination. Other nucleophiles such as allyl or iodine were available for this methodology. The moderate Lewis acidity of indium catalyst enabled chemoselective reaction, and therefore ester, nitro, cyano, or halogen groups were not affected during the reaction course.     

CH3S与HO2气相反应机理的理论研究

采用密度泛函理论的B3LYP方法, 在6-311＋＋G(d,p)基组水平上研究了CH3S自由基与HO2自由基的微观反应机理, 全参数优化了反应势能面上各驻点的几何构型, 振动分析和内禀反应坐标(IRC)分析结果证实了中间体和过渡态的真实性, 计算所得的键鞍点电荷密度的变化情况也确认了反应过程. 找到了五条可能的反应通道, 对结果的分析表明: 单线态反应通道(5) CH3S＋HO2→CH3SOOH (1P), 是所有通道中的主要反应通道. 该通道不需要克服过渡态能垒, 属于放热反应, 在动力学和热力学上都是最为有利的. 对于三线态反应通道来说, 通道(1)CH3S＋HO2→COM11→TS1→COM12→CH3SH＋O2 (3P)为主要反应通道, 控制步骤的活化能为53.5 kJ/mol, 能垒最低, 属于放热反应, 在动力学和热力学上都是有利的.     

Infrared matrix isolation study of the thermal and photochemical reactions of ozone with dimethylzinc

The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to explore the reaction of (CH3)2Zn with O3 over a range of time scales. Upon twin jet deposition, an initial cage pair complex was observed, along with formation of the novel H3COZnCH3 species. Subsequent UV irradiation destroyed the complex and greatly increased the yield of H3COZnCH3. An extensive set of bands were seen for this molecule, and (18)O spectroscopic data were obtained as well. The identification of this species was supported by theoretical calculations at the B3LYP/6-311++g(d,2p) level. Merged jet deposition led to a very different set of products, including H2CO, CH3OH and C2H6, identifications that were confirmed by (18)O substitution. In addition, a new variable length concentric deposition technique was developed to permit study of the time scales between twin (relatively short) and merged (relatively longer) reaction times. Mechanistic inferences for this reaction are discussed.     

芳羧酸功能化聚苯乙烯的制备及其与Tb(Ⅲ)离子配合物荧光发射特性初探

通过氯甲基苯甲酸(CMBA)的Friedel-Crafts 烷基化反应,对聚苯乙烯(PS)进行了功能化改性,将苯甲酸(BA)键合在聚苯乙烯侧链,制得了改性聚苯乙烯(BAPS),采用红外光谱、核磁共振氢谱及紫外吸收光谱等测试技术对其进行了结构表征,考察了影响CMBA与PS之间Friedel-Crafts烷基化反应的主要因素。 结果表明,适宜的反应条件为:70 ℃,以N,N-二甲基乙酰胺为溶剂,SnCl4为催化剂。 使BAPS与Tb(Ⅲ)离子配位,制得高分子-稀土配合物BAPS-Tb(Ⅲ),该配合物不仅发射出Tb3+离子的特征荧光,而且大分子配基BAPS对Tb3+离子的荧光发射显示出很强的敏化作用。     

Regioselective addtion of 5-amino-3-benzylthio-1,2,4-triazole and its analogues with aryl isocyanates

The orientation of the addition of 5-amino-3-benzylthio-1,2,4-triazole and its analogues (pyrazole) (1) with the aryl isocyanate can be directed by controlling the reaction temperature and one of the product, 5-amino-1-arylaminocarbonyl-3-benzylthio-1,2,4-triazole (pyrazole) (2), can rearrange at 170°C to another product, 5-arylureylene-3-benzylthio-1,2,4-triazole (pyrazole) (3). A plausible mechanism explanation for this rearrangement reaction was presented. It was suggested that the rearrangement reaction could be referred to the thermodynamics transposition leading to the predominant 5-arylureylene-3-benzylthio-1,2,4-triazole energy preferentially.     

From allylic alcohols to aldols by using iron carbonyls as catalysts: computational study on a novel tandem isomerization-aldolization reaction

The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde.     

Binuclear cyclometalated organoplatinum complexes containing 1,1'-bis(diphenylphosphino)ferrocene as spacer ligand: kinetics and mechanism of MeI oxidative addition

The binuclear complex [Pt2Me2(ppy)2(mu-dppf)], 1, in which ppy = deprotonated 2-phenylpyridyl and dppf = 1,1'-bis(diphenylphosphino)ferrocene, was synthesized by the reaction of [PtMe(SMe2)(ppy)] with 0.5 equiv of dppf at room temperature. In this reaction when 1 equiv of dppf was used, the dppf chelating complex 2, [PtMe(dppf)(ppy-kappa1C)], was obtained. The reaction of Pt(II)-Pt(II) complex 1 with excess MeI gave the Pt(IV)-Pt(IV) complex [Pt2I2Me4(ppy)2(mu-dppf)], 3. When the reaction was performed with 1 equiv of MeI, a mixture containing unreacted complex 1, a mixed-valence Pt(II)-Pt(IV) complex [PtMe(ppy)(mu-dppf)PtIMe2(ppy)], 4, and complex 3 was obtained. In a comparative study, the reaction of [PtMe(SMe2)(ppy)] with 1 equiv of monodentate phosphine PPh3 gave [PtMe(ppy)(PPh3)], A. MeI was reacted with A to give the platinum(IV) complex [PtMe2I(ppy)(PPh3)], C. All the complexes were fully characterized using multinuclear (1H, 31P, 13C, and 195Pt) NMR spectroscopy, and complex 2 was further identified by single crystal X-ray structure determination. The reaction of binuclear Pt(II)-Pt(II) complex 1 with excess MeI was monitored by low temperature 31P NMR spectroscopy and further by 1H NMR spectroscopy, and the kinetics of the reaction was studied by UV-vis spectroscopy. On the basis of the data, a mechanism has been suggested for the reaction which overall involved stepwise oxidative addition of MeI to the two Pt(II) centers. In this suggested mechanism, the reaction proceeded through a number of Pt(II)-Pt(IV) and Pt(IV)-Pt(IV) intermediates. Although MeI in each step was trans oxidatively added to one of the Pt(II) centers, further trans to cis isomerizations of Me and I groups were also identified. A comparative kinetic study of the reaction of monomeric platinum(II) complex A with MeI was also performed. The rate of reaction of MeI with complex 1 was some 3.5 times faster than that with complex A, indicating that dppf in the complex 1, as compared with PPh 3 in the complex A, has significantly enhanced the electron richness of the platinum centers.     

Efficient synthesis of 3H-imidazo[4,5-b]pyridines from malononitrile and 5-amino-4-(cyanoformimidoyl)imidazoles

1-Aryl-5-amino-4-(cyanoformimidoyl)imidazoles 2 were reacted with malononitrile under mild experimental conditions and led to 3-aryl-5,7-diamino-6-cyano-3H-imidazo[4,5-b]pyridines 5, when the reaction was carried out in the presence of DBU, or to 3-aryl-5-amino-6,7-dicyano-3H-imidazo[4,5-b]pyridines 3, in its absence. Both reactions evolved from the adduct formed by nucleophilic attack of the malononitrile anion to the carbon of the cyanoformimidoyl substituent. A 5-amino-1-aryl-4-(1-amino-2,2-dicyanovinyl)imidazole 4 was isolated when this reaction was carried out in the presence of DBU. The structure of compound 4 was confirmed by spectroscopic methods and by reaction with triethyl orthoformate and with acetic anhydride, leading respectively to 9-aryl-6-(cyanomethylidene)purines 11 and 12. Imidazole 2b was also reacted with ethyl acetoacetate, a carbon acid with a pK(a) comparable to that of malononitrile. Similar reaction conditions were used and the product isolated was a 6-carbamoyl-1,2-dihydropurine 10, showing that a different mechanism was operating in this case.     

Formation of Naphthoquinone Oxo-Pyridinium Inner Salts

When 2-chloro-3-(substitued phenoxy)naphthazarine (1) was treated with pyridine or substituted pyridine at elevated temperature, an unexpected reaction took place. The product was identified as 5,8-Dihydroxy-1,4-dioxo-3-(substituted pyridinium)-2-naphthoxide (3, 4). A reaction mechanism for the formation of this product was postulated.     

Regioselective addtion of 5-amino-3-benzylthio-l,2,4-triazole and its analogues with aryl isocyanates

The orientation of the addition of 5-amino-3-benzylthio-1,2,4-triazole and its analogues (pyrazole) (1) with the aryl isocyanate can be directed by controlling the reaction temperature and one of the product, 5-amino-1-arylaminocarbonyl-3-benzylthio-1,2,4-triazole (pyrazole) (2), can rearrange at 170C to another product, 5-arylureylene-3-benzylthio-1,2,4-triazole (pyrazole) (3). A plausible mechanism explanation for this rearrangement reaction was presented. It was suggested that the rearrangement reaction could be referred to the thermodynamics transposition leading to the predominant 5-arylureylene-3-benzylthio-1,2,4-triazole energy preferentially.     

Thermal decomposition of trimethylgallium Ga(CH3)3: a shock-tube study and first-principles calculations

The thermal decomposition of Ga(CH3)3 has been studied both experimentally in shock-heated gases and theoretically within an ab-initio framework. Experiments for pressures ranging from 0.3 to 4 bar were performed in a shock tube equipped with atomic resonance absorption spectroscopy (ARAS) for Ga atoms at 403.3 nm. Time-resolved measurements of Ga atom concentrations were conducted behind incident waves as well as behind reflected shock waves at temperatures between 1210 and 1630 K. The temporal variation in Ga-atom concentration was described by a reaction mechanism involving the successive abstraction of methyl radicals from Ga(CH3)3 (R1), Ga(CH3)2 (R2), and GaCH3 (R3), respectively, where the last reaction is the rate-limiting step leading to Ga-atom formation. The rate constant of this reaction (R3) was deduced from a simulation of the measured Ga-atom concentration profiles using thermochemical data from ab-initio calculations for the reactions R1 and R2 as input. The Rice-Ramsperger-Kassel-Marcus (RRKM) method including variational transition state theory was applied for reaction R3 assuming a loose transition state. Structural parameters and vibrational frequencies of the reactant and transition state required for the RRKM calculations were obtained from first-principles simulations. The energy barrier E3(0) of reaction R3, which is the most sensitive parameter in the calculation, was adjusted until the RRKM rate constant matched the experimental one and was found to be E(0) = 288 kJ/mol. This value is in a good agreement with the corresponding ab-initio value of 266 kJ/mol. The rate constant of reaction R3 was found to be k 3/(cm(3) mol(-1)s(-1)) = 2.34 x 10(11) exp[-23330(K/ T)].