Energy of the C = C Double Bond

Determination of the bond energy as the difference between the experimental energy of the double bond and standard value of the C-C bond energy does not take into account changes in the energy of the C-C bond as it becomes shorter. The change in the single bond energy upon its shortening by 0.2 Å was evaluated from the compressibilities of diamond and polyethylene, and also by quantum-chemical calculations. With this value taken into account, the energies of the and bonds in ethylene become close, which proves the equivalence of the traditional and banana models of the C = C bond.     

Stereoselective synthesis of the C21C27 fragment of the phorboxazoles

A stereoselective synthesis of the C21C27 fragment of phorboxazoles A and B was achieved in 12 linear steps via an intramolecular cyclization induced by mercury acetate, to afford a functionalized tetrahydropyran.     

Stereoselective synthesis of the C1–C12 fragment of the thuggacins

A concise asymmetric synthesis of the C1–C12 fragment of the antibacterial natural product thuggacins has been achieved. The stereochemistry of this fragment was established efficiently via stereoselective reduction and Evans-aldol condensation. Hanztsch’s method and a Horner–Wadsworth–Emmnons reaction were employed for thiazole formation and the construction of the E-α,β-unsaturated double bond.     

Conversion of C5 into C6 cyclic species through the formation of C7 intermediates

We have recently proposed that the addition of C2H2 to the cyclopentadienyl radical can lead to the rapid formation of the cycloheptatrienyl radical and, in succession, of the indenyl radical. These reactions represent an interesting and unexplored route for the enlargement of gas-phase cyclic species. In this work we report ab initio calculations we performed with the aim of investigating in detail the gas-phase reactivity of cycloheptatrienyl and indenyl radicals. We found that the reaction of the cycloheptatrienyl radical with atomic hydrogen can lead to its fast conversion into the more stable benzyl radical. This reaction pathway involves the intermediate formation of heptatriene, norcaradiene, and toluene. Successively we investigated whether this reaction mechanism can be extended to polycyclic aromatic hydrocarbons (PAHs). For this purpose we studied the reaction of C2H2 with the indenyl radical, which can be considered as a superior homologue of the cyclopentadienyl radical. This reaction proceeds through a pathway similar to that proposed for C5H5 but with a reaction rate about an order of magnitude smaller. The present calculations extend thus the previously proposed C5-C7-C9 mechanism to bicyclic PAH and suggest a fast route for the conversion of C5 into C6 cyclic radicals, mediated by the formation of C7 cyclic species.     

Structure and stability of the defect fullerene clusters of C60: C59, C58, and C57

We have performed density functional calculations for the structures and stabilities of various isomers of the defect fullerene clusters of C(60): C(59), C(58), and C(57). The C(59_)5-8, C(58_)5-5-7, and C(57_)4-5-9 clusters were calculated to be the most stable isomers of the C(59), C(58), and C(57) clusters, respectively. There are obvious relationships between structure and stability of the defect fullerene clusters. First, an unsaturated carbon atom favors being located at a 6-membered ring rather than a 5-membered ring. Second, the most stable isomers prefer to have newly formed 5-membered rings, rather than newly formed 4-membered rings.     

Gas phase electronic spectra of the carbon chains C5, C6, C8, and C9

Three electronic absorption systems for C5 at 511, 445, and 232 nm and one for C6, C8, and C9 centered at 228, 259, and 288 nm have been observed in the gas phase. The C5 chain was produced in both discharge and ablation sources and detected using resonant two-color two-photon ionization spectroscopy involving 10.5 eV photons. The decay of the excited singlet electronic states indicates fast intramolecular processes on a subpicosecond time scale. The internal energy is assumed to be trapped in a triplet state for at least 15 micros. Hole-burning experiments on the 2 (3)Sigma(u)- <-- X (3)Sigma(g)- transition of C6, C8, and (1)Sigma(u)+ <-- X (1)Sigma(g)+ of C9 confirm the predissociative nature of the excited electronic states.     

Studies of the photoexcited states of the fullerenes, C60 and C70

The spectra of C₆₀ and C₇₀ were examined using low-temperature photoluminescence and quasi-elastic light scattering spectroscopy. A detailed vibronic analysis of the lowest triplet and singlet excited states of C₇₀ is obtained. The lowest triplet state is identified as a ³E₁′ state and the vibronic structure consists primarily of Herzberg-Teller active e₂′ modes. The intensity of the electronic origin is comparable to the vibronically induced intensity and is extraordinarily solvent sensitive. The spectrum of monosubstituted C₆₀ is shown to be qualitatively similar to that of C₆₀ in polar or strongly complexing solvents. The principal effect of solvent interaction or substitution is to induce dipole intensity in the orbitally forbidden electronic origins of the luminescent states of C₆₀ and C₇₀. The Rayleigh scattering of fullerene solutions illustrates that solute aggregation occurs easily and that aggregate nucleation is strongly affected by surfaces in contact with the solution.     

Rationalizing the AlI-Promoted Oxidative Addition of C−C Versus C−H Bonds in Arenes

The factors controlling the oxidative addition of C−C and C−H bonds in arenes mediated by Al^I have been computationally explored by means of Density Functional Theory calculations. To this end, we compared the processes involving benzene, naphthalene and anthracene which are promoted by a recently prepared anionic Al^I-carbenoid. It is found that this species exhibits a strong tendency to oxidatively activate C−H bonds over C−C bonds, with the notable exception of benzene, where the C−C bond activation is feasible but only under kinetic control reaction conditions. State-of-the-art computational methods based on the combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis have been used to rationalize the competition between both bond activation reactions as well as to quantitatively analyze in detail the ultimate factors controlling these transformations.     

Switching the Statistical C3/C1 Ratio in the Threefold Aromatic Substitution of Tribenzotriquinacenes towards the C3 Isomer

Tribenzotriquinacene (TBTQ) is a bowl‐shaped molecule that has been widely used as a molecular building block in supramolecular and materials chemistry. Especially C₃‐symmetric threefold‐substituted TBTQs are interesting for these purposes. Until now a general and selective synthetic approach to those C₃‐symmetric products was lacking, mainly because the typically used electrophilic aromatic substitution reactions of the parent TBTQ hydrocarbons produce predominantly the C₁ isomer over the C₃ isomer (3:1 statistical ratio). Herein we introduce a threefold borylation of TBTQ with the C₃ isomer as the main product (2.6:1 C₃/C₁ ratio). The borylated TBTQ can be converted in good yields into other C₃‐symmetric TBTQs, thus allowing straightforward synthetic access to new building blocks for supramolecular and materials chemistry.     

大气中C1～C10羰基化合物的分析测定

利用2,4二硝基苯肼(DNPH)涂布硅胶管采集空气中的C1～C10羰基化合物,经乙腈洗脱后用高效液相色谱-紫外检测器(HPLC/UV)分析检测.吸附管的采集效率>95%,平行样相对标准偏差<10%;化合物的检出限在0.05～0.15μg/m3之间,方法适合于室内和室外环境中低浓度的羰基化合物的测定.     

Synthesis of the C10–C24 fragment of (+)-cannabisativine

The stereoselective synthesis of the C10–C24 fragment of (+)-cannabisativine has been achieved. The key steps involved in this strategy are the Sharpless asymmetric dihydroxylation, the diastereoselective allylation of an imine, and the ring closing metathesis (RCM).     

Enantioselective synthesis of the C8-C20 segment of curvicollide C

The enantioselective synthesis of the C8-C20 fragment of curvicollide C has been accomplished. A catalytic asymmetric Claisen rearrangement (CAC), a diastereoselective methyl cupration of an alkynoate, and a Julia-Kocienski olefination served as key C/C-connecting transformations.     

Stereoselective synthesis of the C3–C12 subunit of laulimalide

A stereoselective synthesis of the C3–C12 subunit of the tumor growth inhibitors laulimalide is disclosed. The key steps of the synthesis include asymmetric alkylation using Oppolzer’s protocol and an asymmetric hetero-Diels–Alder reaction using Jacobsen’s catalyst. Substrate controlled diastereoselective Luche reduction followed by Ferrier type reactions are other key steps.     

Determination of the thermal stability of the fullerene dimers C120, C120O, and C120O2

We have produced the fullerene dimers C(120), C(120)O, and C(120)O(2) by a high-speed vibration milling technique. The thermal stability of C(120), C(120)O, and C(120)O(2) has been studied in the temperature range 150-350 degrees C for up to 4 h under vacuum. The bridging oxygen atoms were found to substantially increase the stability of the fullerene dimer molecules.