- Alkyl and aromatic nitrates in atmospheric particles determined by gas chromatography tandem mass spectrometry
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Organic nitrates in the atmosphere are associated with photochemical pollution and are the main components of secondary organic aerosols, which are related to haze. An efficient method for determining organic nitrates in atmospheric fine particles (PMsub
- Yang, Xinhao,Luo, Feixian,Li, Junqi,Chen, Deyang,Ye,Lin, Weili,Jin, Jun
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- Reactions of Cerium(IV) Ammonium Nitrate with Aromatic Compounds in Acetonitrile. Part 1. The Mechanism of Side-chain Substitution
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Benzene, alkylbenzenes, and phenolic ethers react with cerium(IV) ammonium nitrate in acetonitrile to give nitrocompounds and (if α-hydrogen atoms are present) also the products of side-chain substitution.With many substrates, the major products of side-chain substitution are benzyl nitrates but compounds which can give rise to particularly stable benzyl cations give mainly products from reaction with the solvent.Relative rates of side-chain substitution have been determined by the competition method: the results indicate reaction via a radical cation and the isotope effect kH/kD=2.3 observed in reactions with 10>-p-xylene suggests that proton loss from this radical cation is, at least partly, rate-determining.
- Dinctuerk, Suphi,Ridd, John H.
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- Establishment of heterolytic and homolytic Y-NO2 bond dissociation energy scales of nitro-containing compounds in acetonitrile: Chemical origin of NO2 release and capture
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(Chemical Equation Presented) The first heterolytic and homolytic N(O)-NO2 bond dissociation energy scales of three types Y-nitro (Y = N, O) compounds and corresponding radical anions in acetonitrile were established by using titration calorimetry combined with relevant electrochemical data through proper thermodynamic cycles.
- Li, Xin,Zhu, Xiao-Qing,Zhang, Fan,Wang, Xiao-Xiao,Cheng, Jin-Pei
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p. 2428 - 2431
(2008/09/20)
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- Mechanistic duality of the side-chain substitution in electrophilic aromatic nitration. Unexpected large difference in deuterium isotope effect k(H)/k(D) between the side-chain nitration and nitrooxylation of deuterated p-xylenes
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A large difference in deuterium kinetic isotope effect observed between the side-chain nitration and nitrooxylation of deuterated p-xylenes, 1,4- (CH3)(CD3)C6H4 and 1,4-(CD3)2C6D4, suggests the operation of different mechanisms for these two types of side-chain substitution.
- Nonoyama, Nobuaki,Iwaya, Masao,Suzuki, Hitomi
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p. 229 - 233
(2007/10/03)
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- CERIUM (IV) AMMONIUM NITRATE CATALYSED PHOTOCHEMICAL AUTOXIDATION OF ALKYLBENZENES
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The autoxidation of alkylbenzenes can be promoted photochemically in the presence of catalytic amounts of cerium (IV) ammonium nitrate (CAN) under very mild conditions, the efficiency of the process being significantly increased by added acids.It is suggested that the reaction is promoted by NO3 radicals formed in the light induced decomposition of CAN and that Ce(III) may be reoxidized to Ce(IV) by benzylperoxy radicals.
- Baciocchi, E.,Giacco, T. Del,Sebastiani, G. V.,Rol, C.
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p. 3353 - 3356
(2007/10/02)
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- Anionic Surfactants Catalysis in the Two-phase Oxidation of Toluene Derivatives with Cerium Ammonium Nitrate. A Facile Synthesis of Some Benzaldehydes
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The catalytic activity of sodium 1-dodecanesulfonate, sodium dodecyl sulfate, disodium 2-dodecyl-1,3-propanediyl disulfate (1) and trisodium 2,2-bis(sulfonatemethyl)tetradecylsulfate(2) was tested in the two-phase oxidation of p-xylene with cerium ammonium nitrate (CAN).Also various tolouene derivatives were oxidized with CAN in the presence of sodium dodecyl sulfate.The observed reaction enhancements are discussed in terms of the micelle-substrate interaction.The catalytic oxidation of some toluene derivatives (3) with a subsequent thermal rearrangement of the oxida tion product offers a simple synthetic route to benzaldehydes 4.
- Skarzewski, Jacek,Mlochowski, Jacek
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p. 963 - 967
(2007/10/02)
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- THE ROLE OF NITRATE FREE RADICALS IN THE PHOTOCHEMICAL SIDE-CHAIN NITROOXYLATION OF ALKYLBENZENES BY CERIUM(IV) AMMONIUM NITRATE IN ACETONITRILE
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It is suggested that the reactive species in the CAN-induced photochemical side-chain nitrooxylation of alkylbenzenes is the nitrate radical, which probably acts as one-electron oxidant.
- Baciocchi, E.,Giacco, T. Del,Rol, C.,Sebastiani, G. V.
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p. 541 - 544
(2007/10/02)
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- TWO-PHASE OXIDATION OF SOME AROMATIC COMPOUNDS WITH CERIUM AMMONIUM NITRATE IN THE PRESENCE OF SURFACTANTS.
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The two-phase oxidations of 3,6-dimethoxydurene and xylenes in cyclohexane solutions with the aqueous solution of cerium ammonium nitrate were carried out in the presence of cationic, nonionic, and anionic surfactants. Both cationic (ammonium salt) and nonionic (Dipodand) surfactants inhibited the reaction. The anionic surfactant (sodium dodecyl sulfate, SDS) catalyzed these oxidations. From the product distribution it was concluded that the catalytic action of SDS is due to the binding of aromatic compounds and the Ce(IV) ions to the surface of the SDS micelles. The micellar oxidant has the high oxidation potential which should allow to oxidize the comparatively nonreactive substrates.
- Skrzewski,Cichacz
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p. 271 - 274
(2007/10/02)
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- PHOTOCHEMICAL NITROOXYLATION OF METHYLBENZENES BY CERIUM(IV) AMMONIUM NITRATE IN ACETONITRILE
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The photochemical reaction of substituted toluenes with CAN in CH3CN leads to good yields of benzyl nitrates under very mild conditions.
- Baciocchi, E.,Rol, C.,Sebastiani, G. V.,Serena, B.
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p. 1945 - 1946
(2007/10/02)
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- Reactions of Cerium(IV) Ammonium Nitrate with Aromatic Compounds in Acetonitrile. Part 2. Nitration; Comparison with Reactions of Nitric acid
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The nitration of benzene and a number of alkylbenzenes by cerium(IV) ammonium nitrate in acetonitrile shows the same intra- and inter-molecular selectivity as nitration with nitric acid under the same conditions but the extent of the other products formed in the two sets of reactions is very different.Nitration by cerium(IV) ammonium nitrate (but not side-chain substitution) is suppressed by the addition of water.The results suggest that these nitration reactions by cerium(IV) ammonium nitrate occur through the intermediate formation of a nitronium ion from the cerium(IV) complex but the order with recpect to the aromatic compound shows that this nitronium ion must then be formed in the presence of the aromatic substrate as a 'spectator'.The relative reactivities with respect to benzene in the nitration of anisole and naphthalene are much greater than those observed in nitration by nitric acid and, with both, the isomer proportions are also anomalous.
- Dinctuerk, Suphi,Ridd, John H.
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p. 965 - 970
(2007/10/02)
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- A NOVEL CLEAVAGE WITH NITRIC ACID OF POLYMETHYLATED DIBENZYL SELENIDES AND SELENOXIDES
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When treated with nitric acid at low temperature, the title selenides and selenoxides undergo a novel cleavage reaction to give the corresponding benzyl nitrates and elemental selenium.
- Suzuki, Hitomi,Ohnishi, Kazumasa
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p. 111 - 112
(2007/10/02)
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- Mercury-assisted solvolyses of alkyl halides. Simple procedures for the preparation of nitrate esters, acetate esters, alcohols and ethers
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The reactions of a wide variety of alkyl halides with mercury(I) and/or (II) nitrate in 1,2-dimethoxyethane, mercury(II) acetate in acetic acid, aqueous mercury(II) perchlorate, and mercury(II) perchlorate in alcohol solvents have been investigated; as a result, simple high yield procedures for the conversion of alkyl halides into the corresponding nitrate esters, acetate esters, alcohols and ethers have been developed.
- McKillop,Ford
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p. 2467 - 2475
(2007/10/05)
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