- Reactions of atomic carbon with acyl chlorides
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Reactions of arc-generated carbon atoms with acyl chlorides proceed by two distinct mechanistic pathways depending on the nature of the alkyl group in the substrate. Acetyl chloride affords vinyl chloride from the putative chloromethylcarbene produced by deoxygenation, whereas pivaloyl chloride gives t-butyl chloride as the predominant product via a chain reaction from the initially generated pivaloyl radical. When the alkyl group is isopropyl, both pathways are implicated.
- Herrick, Daniel B.,Thamattoor, Dasan M.,Shevlin, Philip B.
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scheme or table
p. 6036 - 6038
(2009/04/04)
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- A nonspectroscopic method to determine the photolytic decomposition pathways of 3-chloro-3-alkyldiazirine: Carbene, diazo and rearrangement in excited state
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C60 acts as a mechanistic probe for the formation of carbene, diazo compound, and for the rearranged product via the excited state in the photolysis of 3-chloro-3-isopropyldiazirine and 3-chloro-3-chloromethyldiazirine. The carbene adds to C60 to form methanofullerene, whereas the diazo compound adds to C60 to form fulleroid. The olefin product arises as a result of the rearrangement in the excited state.
- Wakahara, Takatsugu,Niino, Yasuyuki,Kato, Takashi,Maeda, Yutaka,Akasaka, Takeshi,Liu, Michael T. H.,Kobayashi,Nagase
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p. 9465 - 9468
(2007/10/03)
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- Reactions of 2,2-dialkylvinyl iodonium salt with halide ions
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Reactions of (E)- and (Z)-2-methyl-5-phenyl-1-pentenyl(phenyl)iodonium (1) salts with halide ions were examined in various solvents at 50 or 60°C. The main products are those of substitution, 1-halo-2-methyl-5-phenyl-1-pentenes, mainly of inversion but involving some retained products. Varying amounts of rearranged products are also formed. Reaction follows pseudo-first-order kinetics at [1] a pre-equilibrium formation of the adduct, λ 3-haloiodane, and first-, second-, and third-order reaction pathways. The first-order rate constant for the E isomer, (E)-1, is greater than that for (Z)-1, while the opposite is the case for the second- and third-order terms. The main reaction is considered to proceed via a vinylic in-plane S(N)2 mechanism to lead to inversion while some retention routes via out-of-plane S(N)2 and/or ligand coupling mechanism are also possible. Competing rearrangement reactions occur by the β-alkyl participation and no evidence for formation of the primary vinylic cation was obtained.
- Okuyama, Tadashi,Sato, Koichi,Ochiai, Masahito
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p. 2341 - 2349
(2007/10/03)
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- Quaternary ammonium polychlorides as efficient reagents for chlorination of unsaturated compounds
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Chlorination of unsaturated compounds by benzyltributylammonium polychlorides results in higher yields of addition products compared to those obtained with molecular chlorine.
- Zelikman,Tyurin,Smirnov,Zyk
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p. 1541 - 1546
(2007/10/03)
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- Synthesis and Characterization of Polychlorinated Isobutenes
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The preparation of polychlorinated methallylic chlorides by continuous chlorination of isobutene with different ratios of chlorine and following HCl-elimination is described.The structure is proved by reaction of the polychlorinated isobutenes with sodium thiolacetate and potassium thiocyanate and by spectroscopic methods.
- Schulze, K.,Hartmann, S.,Krueger, H.,Muehlstaedt, M.,Richter, C.,Richter, H.
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p. 433 - 442
(2007/10/02)
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