- Alkyl and aromatic nitrates in atmospheric particles determined by gas chromatography tandem mass spectrometry
-
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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p. 2762 - 2770
(2019/11/22)
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- USE OF NITROOXY ORGANIC MOLECULES IN FEED FOR REDUCING METHANE EMISSION IN RUMINANTS, AND/OR TO IMPROVE RUMINANT PERFORMANCE
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The present invention relates to a method for reducing the production of methane emanating from the digestive activities of a ruminant and/or for improving ruminant animal performance by using, as active compound at least one organic molecule substituted at any position with at least one nitrooxy group, or a salt thereof, which is administrated to the animal together with the feed. The invention also relates to the use of these compounds in feed and feed additives such as premix, concentrates and total mixed ration (TMR) or in the form of a bolus.
- -
-
Paragraph 0130; 0131
(2014/06/11)
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- Generation and cross-coupling of benzyl and phthalimide-N-oxyl radicals in a cerium(IV) ammonium nitrate/N-hydroxyphthalimide/ArCH2R system
-
A method was developed for the cross-dehydrogenative coupling of alkylarenes and related compounds with N-hydroxyphthalimide (NHPI) using cerium(IV) ammonium nitrate (CAN) to prepare O-substituted NHPI derivatives. The characteristic feature of the reaction is that NHPI plays a dual role. Thus, in the presence of CAN, NHPI generates the phthalimide-N-oxyl (PINO) radical, which abstracts a hydrogen atom from the benzyl position to form a C-centered radical. The target oxidative cross-coupling product is formed mainly through the recombination of PINO with the C-centered radical. Therefore, NHPI serves as a mediator for the radical process and a reagent for the radical cross-coupling. The target products were obtained in yields from 35 to 80%.
- Terent'ev, Alexander O.,Krylov, Igor B.,Sharipov, Mikhail Y.,Kazanskaya, Zoya M.,Nikishin, Gennady I.
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p. 10263 - 10271,9
(2012/12/12)
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- Direct oxidative installation of nitrooxy group at benzylic positions and its transformation into various functionalities
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C-H Nitrooxylation at benzylic positions has been achieved by employing the N-hydroxyphthalimide (NHPI) catalyst/cerium(IV) ammonium nitrate (CAN) reagent system. The nitrooxy groups were demonstrated to function as tentative hydroxy protecting groups, as well as excellent leaving groups for N- and C-substitution reactions. Hence, the present method offers a unique way to synthesize diverse O-, N-, or C-functionalized benzylic compounds from simple alkyl aromatics.
- Kamijo, Shin,Amaoka, Yuuki,Inoue, Masayuki
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supporting information; experimental part
p. 4654 - 4657
(2011/09/30)
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- Aerobic alcohol oxidations mediated by nitric acid
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A touch of acid: Catalytic amounts of HNO3 can trigger the aerobic oxidation of alcohols in the presence of the solid acid amberlyst-15. The desired oxidation cycle, mediated by (H)NOx species, is in kinetic competition with the detr
- Aellig, Christof,Girard, Christophe,Hermans, Ive
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supporting information; experimental part
p. 12355 - 12360
(2012/02/01)
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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
-
(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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- NO donors. Part 16: Investigations on structure-activity relationships of organic mononitrates reveal 2-nitrooxyethylammoniumnitrate as a high potent vasodilator
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The vasoactive properties of 14 organic mononitrates were investigated in vitro using PGF2α-precontracted porcine pulmonary arteries. A surprisingly wide range of vasorelaxant potencies was observed (pD2: 3.36-7.50). Activities showed to be highly sensitive to the molecular structure and the substituents at the molecular carrier of the nitrate group. A correlation between lipophilicity and vasorelaxant potency could not be recognized. 2-Nitrooxyethylammoniumnitrate (1) was found to be slightly superior to the high potency trinitrate GTN.
- Koenig, Andreas,Roegler, Carolin,Lange, Kathrin,Daiber, Andreas,Glusa, Erika,Lehmann, Jochen
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p. 5881 - 5885
(2008/03/14)
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- Imidazolium ionic liquids as solvents for cerium(IV)-mediated oxidation reactions
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Use of imidazolium ionic liquids as solvents for organic transformations with tetravalent cerium salts as oxidizing agents was evaluated. Good solubility was found for ammonium hexanitratocerate(IV) (ceric ammonium nitrate, CAN) and cerium(IV) triflate in 1-alkyl-3-methylimidazolium triflate ionic liquids. Oxidation of benzyl alcohol to benzaldehyde in 1-ethyl-3-methylimidazolium triflate was studied by in-situ FTIR spectroscopy and 13C NMR spectroscopy on carbon-13-labeled benzyl alcohol. Careful control of the reaction conditions is necessary because ammonium hexanitratocerate(IV) dissolved in an ionic liquid can transform benzyl alcohol not only into benzaldehyde but also into benzyl nitrate or benzoic acid. The selectivity of the reaction of cerium(IV) triflate with benzyl alcohol in dry ionic liquids depends on the degree of hydration of cerium(IV) triflate: anhydrous cerium(IV) triflate transforms benzyl alcohol into dibenzyl ether, whereas hydrated cerium(IV) triflate affords benzaldehyde as the main reaction product. Reactions of ammonium hexanitratocerate(IV) with organic substrates other than benzyl alcohol have been explored. 1,4-Hydroquinone is quantitatively transformed into 1,4-quinone. Anisole and naphthalene are nitrated. For the cerium-mediated oxidation reactions in ionic liquids, high reaction temperatures are an advantage because under these conditions smaller amounts of byproducts are formed.
- Mehdi, Hasan,Bodor, Andrea,Lantos, Diana,Horvath, Istvan T.,De Vos, Dirk E.,Binnemans, Koen
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p. 517 - 524
(2007/10/03)
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- Generation of oxynitrenes and confirmation of their triplet ground states
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New sulfoximine- and phenanthrene-based photochemical precursors to oxynitrenes have been developed. These precursors have been used to examine the chemistry and spectroscopy of oxynitrenes. The first EPR spectra of oxynitrenes are reported and are consistent with their triplet ground states. Additional support for the triplet ground state of oxynitrenes is provided by trapping and reactivity studies, nanosecond time-resolved IR investigations, and computational studies.
- Wasylenko, Walter A.,Kebede, Naod,Showalter, Brett M.,Matsunaga, Nikita,Miceli, Alexander P.,Liu, Yonglin,Ryzhkov, Lev R.,Hadad, Christopher M.,Toscano, John P.
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p. 13142 - 13150
(2008/03/11)
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- Preparation of alkyl nitrates, nitrites, and thiocyanates from alcohols utilizing trichloroisocyanuric acid with triphenylphosphine
-
Alcohols in acetonitrile are converted into alkyl nitrates, nitrites, or thiocyanates by the action of triphenylphosphine and trichloroisocyanuric acid along with silver nitrate, silver nitrite, or sodium thiocyanate, respectively.
- Hiegel, Gene A.,Nguyen, Jeremiah,Zhou, Yan
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p. 2507 - 2511
(2007/10/03)
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- NO donors, part 8 [1]: Synthesis and vasodilating activities of substituted benzylnitrates compared to cyclohexylmethylnitrate and GTN
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A series of substituted benzylnitrates (1) and the formally but not chemically similar cyclohexylmethylnitrate (CHMN) have been synthesised. Vasodilating activities were measured on endothelium-intact and NG-nitro-L-arginine (L-NNA)-blocked porcine right coronary arteries, precontracted with prostaglandin F2α (PGF2α). Glyceroltrinitrate (GTN) was used as reference. In intact coronary arteries the vasodilating activities of all benzylnitrates are lower compared with GTN, but higher compared with CHMN. However, blocking the function of the endothelium by L-NNA, the activity of all benzylnitrates increased, whereas that of CHMN and GTN remained nearly unaffected. Under these conditions, the mononitrates 4-nitro-benzylnitrate (1c) and 4-nitrooxymethyl-benzonitrile (1h) even showed higher vasodilator activities than the trinitrate GTN and in general, vasorelaxation by the benzylnitrates as defined by the concentrations for half maximal effects (EC50 values) was found to be 2-3 orders of magnitude higher than that induced by CHMN. The study demonstrates that the in vitro activities of organic nitrates do not correlate with the number of nitrate groups within the molecule nor to the lipophilicity of the molecules. Instead, vasodilator activity is highly sensitive to the structure and the type of the substituents in the molecular carrier of the nitrate group.
- Wessler, Christoph,Homann, Alexander,Fricke, Uwe,Lehmann, Jochen
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p. 581 - 586
(2007/10/03)
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- Oxidation of benzylic alcohols and ethers to carbonyl derivatives by nitric acid in dichloromethane
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Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as - in the case of aldehydes - any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non-benzylic substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Strazzolini, Paolo,Runcio, Antonio
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p. 526 - 536
(2007/10/03)
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- Synthesis and uptake of nitric oxide-releasing drugs by the P2 nucleoside transporter in trypanosoma equiperdum
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A series of S-nitrosothiols, structurally related to the NO-donor S-nitroso-N-acetylpenicillamine, and of organic nitrate esters that contain amidine groups which specify a recognition via the trypanosomal purine transporter P2, were synthesized and tested for their ability to inhibit the uptake of [2-3H]adenosine on Trypanosoma equiperdum. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Soulere, Laurent,Hoffmann, Pascal,Bringaud, Frederic,Perie, Jacques
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p. 1347 - 1350
(2007/10/03)
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- A New Method for Selective Conversion of Alcohols to Nitrates under Mild and Neutral Conditions
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Treatment of alcohols with triphenylphosphine, N-bromosuccinimide (a positive halogen source), and silver nitrate affords the corresponding alkyl nitrates in excellent yields. - Keywords: Alkyl nitrates; alkoxyphosphonium salts; triphenylphosphine; N-bromosuccinimide; alcohols; Selective replacement of hydroxy groups by nitrate groups
- Froeyen, Paul
-
-
- Simple and rapid determination of the activation parameters of organic reactions by temperature-dependent NMR spectroscopy II. Application to reversible reactions
-
A non-isothermal (NIT) method for evaluating the activation enthalpies and entropies of reactions in solutions was applied to several reversible reactions. This was realized by a stepwise elevation of the temperature of a reaction system using a variable-temperature apparatus comprising on NMR spectrometer and a quick collection of FID (free induction decay) at every plateau of the step. The rate from NIT experiments agreed well with the previously measured rates by the conventional methods.
- Satoh, Masahiro,Hirota, Minoru
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p. 2619 - 2624
(2007/10/03)
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- Nitration of Nonactivated Arenes with a Ternary System NO-NO2-O2. Mechanistic Implications of the Kyodai-nitration
-
The ternary mixture NO-NO2-O2 has been found to be more effective than the binary mixture NO2-O2 as a nitrating agent for nonactivated arenes, such as toluene and chlorobenzene; the results may be rationalized in terms of an initial electron transfer mechanism in which nitrogen trioxide, formed from nitrogen monoxide and dioxygen, oxidizes the arene to its racical cation.
- Suzuki, Hitomi,Mori, Tadashi
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p. 291 - 294
(2007/10/02)
-
- Aromatic Nitration under Neutral Conditions Using Nitrogen Dioxide and Ozone as the Nitrating Agent. Application to Aromatic Acetals and Acylal
-
Cyclic acetals derived from aromatic carbonyl compounds can be nitrated smoothly with nitrogen dioxide in ice-cooled dichloromethane or acetonitrile in the presence of ozone and magnesium oxide to give ortho- and para-nitro derivatives as the major product in good combined yields, the acetal ring as a protective group remaining almost intact.An acylal derived from benzaldehyde similarly undergoes nitration on the aromatic ring to give an isomeric mixture of three nitro compounds, in which the ortho and meta isomers predominate, while aromatic orthoesters are rapidly decomposed to give simply the parent esters.Ring nitration under neutral conditions has been interpreted in terms of a nonclassical mechanism, in which nitrogen trioxide is involved as the initial electrophile.
- Suzuki, Hitomi,Yonezawa, Shuji,Mori, Tadashi
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p. 1535 - 1544
(2007/10/03)
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- New one-pot synthesis of alkyl nitrates from alcohols
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Treatment of alcohols with Ph3P-I2-imidazole followed by 'in situ' reaction of the generated iodides with AgNO3 allows the mild conversion of alcohols into alkyl nitrates. Unlike previous procedures, this one requires no electrophilic nitrating conditions.
- Castedo,Marcos,Monteagudo,Tojo
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p. 677 - 681
(2007/10/02)
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- CARBON SILICON BOND CLEAVAGE IN THE OXIDATION OF BENZYLIC SILANES BY CERIUM(IV) AMMONIUM NITRATE
-
Benzyltrimethylsilanes react with cerium(IV) ammonium nitrate in AcOH to give products of C-Si cleavage (benzyl nitrate and acetate), under very mild conditions and in quantitative yields.The reaction rate is very sensitive to the nature of the ring substituents (ρ= -5.4), which clearly suggests the operation of one electron transfer mechanism.
- Baciocchi, Enrico,Del Giacco, Tiziana,Rol, Cesare,Sebastiani, Giovanni Vittorio
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p. 3573 - 3576
(2007/10/02)
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- An Interpretation of the Puzzling Dichotomy of the Reaction Modes Observed during the Side-chain Nitration of Alkylaromatics
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Nitration of substituted pentamethylbenzenes has been carried out under various conditions using the title nitrating systems in order to elucidate the peculiar dependence of the modes of side-chain substitution on the reagent employed; nitrooxylation with HNO3/CH2Cl2 and nitration with HNO3/(CH3CO)2O.Based on the evidence obtained from product variations with substituents, electrochemical nitrodecarboxylation of arylacetates, and ESR examination of the initial stage of the side-chain reactions, a proposal is made that the side-chain substitution of polysubstituted arenes occurs via a heterolytic path with HNO3/CH2Cl2 and via a homolytic path with HNO3/(CH3CO)2O.
- Suzuki, Hitomi,Koide, Hideki,Taki, Yukiko,Ohbayashi, Eiichi,Ogawa, Takuji
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p. 891 - 894
(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
-
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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- 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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- THE ROLE OF NITRATE FREE RADICALS IN THE PHOTOCHEMICAL SIDE-CHAIN NITROOXYLATION OF ALKYLBENZENES BY CERIUM(IV) AMMONIUM NITRATE IN ACETONITRILE
-
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)
-
- A New Synthesis of Allyl Nitrates from Allylmetal (Group IVb) Compounds and Thallium(III) Nitrate
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A new general method for the synthesis of allyl nitrates is described.Allylmetal (group IVb) compounds, on treatment with thallium(III) nitrate in dioxane, gave the corresponding allyl nitrates in good yields.Keywords - allyl nitrate; thallium(III) nitrate; allylsilane; allylgermane; allylstannane; umpolung.
- Ochiai, Masahito,Fujita, Eiichi,Arimoto, Masao,Yamaguchi, Hideo
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p. 887 - 890
(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)
-
- Nitrosation of the N-Alkyl-O-acylhydroxylamines. A New Deamination Method.
-
The nitrosation of N-alkyl-O-acylhydroxylamines leads to immediate decomposition at dry ice temperatures; the corresponding ester and nitrous oxide are formed.An 18O study has shown that the nitroso-O-acylhydroxylamines fragment directly rather than undergo a rearrangement reaction (as observed with the nitrosoamides).The product yields are respectable, especially at low tempreatures, and the method has promise for the generation of high energy carbonium ions.
- White, Emil H.,Ribi, Max,Cho, Lee K.,Egger, Notker,Dzadzic, Petar M.,Todd, Michael J.
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p. 4866 - 4871
(2007/10/02)
-
- The Synthesis and Application of Novel Nitrating And Nitrosating Agents
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Alcohols and phenols are efficiently nitrated with thionyl chloride nitrate or thionyl nitrate, even in the presence of an aromatic moiety.While thionyl chloride nitrate is suitable for nitration of primary OH-groups in carbohydrates, thionyl nitrate is reactive enough to react with secondary OH-groups as well.These reagents permit the highly selective nitration of the 5'-, 2',5'- and 3',5'-OH-groups of ribonucleosides to produce either mono- or diprotected nitro derivatives in high yields.Carbon acids and the enol form of some ketones are efficiently nitrated with trifluoromethanesulfonyl nitrate/potassium tert-butoxide.Lutidine N-oxide(2,6-(CH3)2C5H3N->O) was found to have marked effect on nitration reactions.Similarly, thionyl chloride nitrite and thionyl nitrite exhibit an excellent capacity for nitrosation of the aforementioned substrates
- Hakimelahi, Gholam H.,Sharghi, Hashem,Zarrinmayeh, Hamide,Khalafi-Nezhad, Ali
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p. 906 - 915
(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
-
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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- 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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p. 961 - 964
(2007/10/02)
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- Reactions of Triphenylphosphine- and Trialkyl Phosphite-Silver Nitrate Complexes with Positive Halogen Compounds. Synthesis of α-Nitro Nitriles
-
The reaction of α-bromo-α-cyano esters, α-bromo-α-cyano nitriles, and α-bromo-α-cyano imides with triphenylphosphine- or trialkyl phosphite-silver nitrate complexes leads to replacement of the positive bromine atom by a nitro group under mild conditions.I
- Ketari, Rachid,Foucaud, Andre
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p. 4498 - 4501
(2007/10/02)
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- Direct vs. Indirect Mechanisms in Organic Electrochemistry. Estimates of Activation Energies for Hydrogen Atom Transfer Processes of Relevance in Indirect Mechanisms Using the Bond Energy-Bond Order (BEBO) and Equibonding Methods
-
Activation energies for a number of hydrogen abstraction reactions of interest in mechanistic organic electrochemistry have been calculated using the bond energy-bond-order (BEBO) and equibonding method.The main emphasis has been put on processes with bearing on the problem of deciding between direct and indirect mechanisms in anodic oxidation, viz. acyloxylation, hydroxylation, methoxylation, nitrooxylation, cyanation, carbomethoxylation and azidation.The results indicate that indirect mechanisms might play a more important role than presently assumed.
- Eberson, Lennart
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p. 481 - 492
(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
-
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
-
p. 2467 - 2475
(2007/10/05)
-